Transition metal compound, catalyst for olefin polymerization and method for producing polyolefin

ABSTRACT

A novel transition metal compound wherein the transition metal belongs to group 4 of the periodic table and the transition metal compound has a hydrogen atom ligand and three cyclopentadienyl ligands comprising at least one substituted cyclopentadienyl ligand. The novel transition metal compound can be used as a component of a catalyst exhibiting high activity for olefin polymerization and is characteristic in containing no halogen element.

TECHNICAL FIELD

This invention relates to a novel transition metal compound, a catalystfor olefin polymerization, and a method for producing polyolefin.

BACKGROUND ART

Many compounds composed of transition metals of group 4 of the periodictable and cyclopentadienyl ligands or substituted cyclopentadienylligands, which are coordinating to the transition metal, have beensynthesized. As well known in the prior art, these compounds are usedfor various organic syntheses such as catalysts for polymerization.(e.g., SYNTHESIS, Jan. 1988, 1–19 and Japanese Patent Laid-OpenPublication No. S58-19309). It is disclosed that the density andmolecular weight of the polymer can be changed inolefin-copolymerization by introducing substituted group into thecyclopentadienyl ligand of transition metal compound. (Japanese PatentPublication No. H7-37488, etc.)

However, most of these transition metal compounds aremono-cyclopentadienyl compounds, mono-substituted cyclopentadienylcompounds, biscyclopentadienyl compounds and bis-substitutedcyclopentadienyl compounds.

There are hitherto several reports concerning triscyclopentadienylcompounds and tris-substituted cyclopentadienyl compounds. They areexemplified by Cp₃ZrCl (Bul. Chem. Soc. Fr., 1978, II-292), Cp₃ZrMe(Organometallics 1997, 16, 531), (MeCp)₃ZrCl (Bul. Chem. Soc. Fr., 1978,II-292), (Me₃SiCp)₃ZrCl (Acta. Cryst., 1995, C51, 10) and Ind₃MCl (M=Zr,Hf) (J. Organomet. Chem., 1997, 544, 139). The number of information ofthis kind is not large.

Concerning the triscyclopentadienyl metal hydride compounds andtris-substituted cyclopentadienyl metal hydride compounds (the metal isa transition metal of group 4 of the periodic table), only CP₃ZrH hasbeen hitherto reported. (The structural analyses by IR spectrometry andRaman spectrometry are reported in J. Organomet. Chem., 1982, 235, 69and the structural analysis by X-ray diffractiometry is reported inOrganometallics, 1999, 18, 3170.) Concerning the method for synthesizingthese compounds, only the reactions of LiAlH₄ with Cp₄Zr and t-BuLi withCp₄Zr are known. In addition to these reactions, the reaction of LiAlH₄with Cp₃ZrCl and the reaction of alkyl lithium with CP₃ZrCl areconsidered. However, intended compounds are hardly obtained throughthese reactions because of the occurrence of a side-reaction to lose Cpligand. Concerning the tetrakis-cyclopentadienyl zirconium compoundwhich has at least one substituted cyclopentadienyl group other thancyclopentadienyl group, the report is hardly found because the repulsionby steric hindrance is largely caused to occur.

In other words, any transition metal compound having at leastone-substituted cyclopentadienyl group among its three cyclopentadienylligands has not been known at all.

The mono-cyclopentadienyl metal compound, bis-cyclopentadienyl metalcompound and triscyclopentadienyl metal compound are generally stable ashalogenides such as chlorides (the metal is a transition metal of group4 of the periodic table). The polyolefin that is polymerized in thepresence of the catalyst of these compounds, contains a trace amount ofhalogen compound resulted from the catalyst. The polyolefin containinghalogen compound, even when the amount is very small, is liable to beoxidized by heat or light rays and yellowing is caused to occur, so thatantioxidant or halogen catcher is often used.

With the increasing tendency to the prevention of environmental problemin recent years, the polyolefin containing no additives such as halogencompound or antioxidant, which gives undesirable influence to humanbody, is largely demanded. Particularly, in the fields of food packagesand medical appliances, the halogen-free or additive-free polyolefin isin great demand. As the metal compounds containing no halogen element,in which the metal is a transition metal of group 4 of the periodictable, there are exemplified by mono-cyclopentadienyl metal alkylcompound and bis-cyclopentadienyl metal alkyl compound. These compoundscan be prepared from corresponding halogenides by using Grignard reagentor alkyl lithium.

Among these compounds, however, most of these compounds having hydrogenatom at β-position are not stable owing to the occurrence of release ofβ-hydrogen atom. Meanwhile, the compounds having no hydrogen atom atβ-position, such as methylated compounds and benzyl compounds can existas thermodynamically stable compounds because they are free from thereleasing of the hydrogen atom at β-position. However, these alkylcompounds must be stored strictly in an inert gas atmosphere, becausethe compounds are liable to react with water or oxygen in the system todecompose even when the content of water or oxygen is very small. Inorder to synthesize the alkyl compound from tris-cyclopentadienyl metalhalide, when the alkylation is carried out by using Grignard reagent oralkyl lithium, which is used in ordinary synthesizing method forcomplexes, the reaction to release one cyclopentadienyl ligand from thethree ligands occurs. Accordingly, it is difficult to synthesize thealkyl compound at high yield through this method.

The present invention provides a novel transition metal compound, whichhas not been known yet. This novel transition metal compound can be anexcellent catalyst exhibiting high polymerizing activity when it is usedas a component of catalyst for olefin polymerization. The new metalcompound contains no halogen element, so that the obtained polyolefincontains no halogen element. Accordingly, the amount of additives can bereduced as compared with conventional polyolefin. In addition, thepolyolefin can also be used without adding any additive. The noveltransition metal compound is composed of a transition metal of group 4of the periodic table, three ligands of cyclopentadienyl derivative andone hydrogen atom. The transition metal compound of this kind has neverbeen known. Furthermore, it has not been known either that thetransition metal compound can be used as a component of catalyst forolefin polymerization.

The novel transition metal compound according to the present inventionis a compound of a metal of group 4 of the periodic table having ligandsof three cyclopentadienyl derivatives and one hydrogen atom, whichcompound contains no halogen element. The transition metal compound ofthis invention is more stable in relation to water and oxygen, ascompared with the dialkylmetallocene of the same metal.

DISCLOSURE OF INVENTION

This invention provides a novel transition metal compound, which can beused as a component of high activity catalyst for polymerization ofolefin containing no halogen element. The compound is composed of atransition metal of group 4 of the periodic table having threecyclopentadienyl ligands and a ligand of hydrogen atom. At least one ofthe three cyclopentadienyl ligands is a substituted cyclopentadienylgroup.

The invention will be described in more detail.

The novel transition metal compound of a first aspect of the presentinvention is represented by the following general formula (1).(C₅R¹R²R³R⁴R⁵)(C₅R⁶R⁷R⁸R⁹R¹⁰)(C₅R¹¹R¹²R¹³R¹⁴R¹⁵)M¹H  Formula (1)[In the formula, (C₅R¹R²R³R⁴R⁵), (C₅R⁶R⁷R⁸R⁹R¹⁰) and (C₅R¹¹R¹²R¹³R¹⁴R¹⁵)denote a cyclopentadienyl group or a substituted cyclopentadienyl group,respectively. R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴ and R¹⁵ are any one of hydrogen atom, hydrocarbon group having 1 to30 carbon atoms or organosilicon group having substituent group ofhydrocarbon having 1 to 30 carbon atoms, which can be the same ordifferent from one another. Any of R¹, R², R³, R⁴ and R⁵; or R⁶, R⁷, R⁸,R⁹ and R¹⁰; or R¹¹R¹², R¹³R¹⁴ and R¹⁵ can be bonded to one anotherforming a cyclic hydrocarbon group (including polycyclic structure).However, at least one of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴ and R¹⁵ must be a substituent group other than a hydrogenatom. M¹ denotes a transition metal of group 4 of the periodic table.]

The transition metal compound of a second aspect of the presentinvention is represented by the following general formula (2).(C₅R¹⁶R¹⁷R¹⁸R¹⁹R²⁰)(C₅R²¹R²²R²³R²⁴R²⁵)(C₅H₂R²⁶R²⁷R²⁸)M²H  Formula (2)[In the formula, C₅R¹⁶R¹⁷R¹⁸R¹⁹R²⁰, C₅R²¹R²²R²³R²⁴R²⁵ and C₅R₂R²⁶R²⁷ R²⁸denote a cyclopentadienyl group or a substituted cyclopentadienyl grouprespectively. R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷and R²⁸ are any one of a hydrogen atom, a hydrocarbon group having 1 to30 carbon atoms or an organosilicon group having substituent of ahydrocarbon having 1 to 30 carbon atoms, which can be the same ordifferent from each other. Among them, any group of R¹⁶, R¹⁷, R¹⁸, R¹⁹and R²⁰; or R²¹, R²², R²³, R²⁴ and R²⁵; or R²⁶, R²⁷ and R²⁸ can bebonded to each other forming a cyclic hydrocarbon group (includingpolycyclic structure). At least one of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹,R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ must be a substituent group otherthan a hydrogen atom. M² denotes a transition metal of group 4 of theperiodic table.]

The transition metal compound of a third aspect of the present inventionis represented by the foregoing general formula (2), wherein R²⁶, R²⁷and R²⁸ are bonded to adjacent carbon atoms of 1-position, 2-positionand 3-position of the transition metal compound.

The transition metal compound of a fourth aspect of the presentinvention is represented by the following general formula (3).(C₅H₂R²⁹R³⁰R31)(C₅H₂R³²R³³R³⁴)(C₅H₂R³⁵R³⁶R³⁷)M³H  Formula (3)[In the formula, (C₅H₂R²⁹R³⁰R³¹), (C₅H₂R³²R³³R³⁴) and (C₅H₂R³⁵R³⁶R³⁷)denote a cyclopentadienyl group or a substituted cyclopentadienyl group,respectively. The symbols R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁶ and R³⁷ areany of a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atomsor an organosilicon group having a substituent of hydrocarbon having 1to 30 carbon atoms, which may be same or different from one another.Furthermore, R²⁹, R³⁰ and R³¹; or R³², R³³ and R³⁴, or R³⁵, R³⁶ and R³⁷can be bonded to one another to form a cyclic hydrocarbon group(including polycyclic structure), however, at least one of R²⁹, R³⁰,R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷ must be a substituent group otherthan a hydrogen atom. The symbol M³ denotes a transition metal of group4 of the periodic table.]

The transition metal compound of a fifth aspect of the present inventionis represented by the foregoing general formula (3), wherein the groupsof R²⁹, R³⁰ and R³¹; R³², R³³ and R³⁴; and R³⁵, R³⁶ and R³⁷ are bondedto adjacent carbon atoms of 1-position, 2-position and 3-position of therespective cyclopentadienyl group.

The transition metal compound of a sixth aspect of the present inventionis represented by the foregoing general formula (3), wherein the threesubstituted cyclopentadienyl groups of (C₅H₂R²⁹R³⁰R³¹), (C₅H₂R³²R³³R³⁴)and (C₅H₂R³⁵R³⁶R37), are same.

The transition metal compound of a seventh aspect of the presentinvention is represented by the following general formula (4).(C₅H₃R³⁸R³⁹)(C₅H₃R⁴R⁴¹)(C₅H₃R⁴²R⁴³)M₄H  Formula (4)[In the formula, the groups of (C₅H₃R³⁸R³⁹), (C₅H₃R⁴⁰R⁴¹) and(C₅H₃R⁴²R⁴³) denote cyclopentadienyl groups or substitutedcyclopentadienyl groups, respectively. The groups of R³⁸, R³⁹, R⁴⁰, R⁴¹,R⁴² and R⁴³ are a hydrogen atom, a hydrocarbon group having 1 to 30carbon atoms or an organosilicon group having a substituent ofhydrocarbon having 1 to 30 carbon atoms, which may be the same ordifferent from one another. Any of R³⁸, R³⁹; or R⁴⁰, R⁴¹; or R⁴², R⁴³can be bonded to each other forming a cyclic hydrocarbon group(including polycyclic structure). At least one of R³⁸, R³⁹, R⁴⁰, R⁴¹,R⁴² and R⁴³ is a substituent other than a hydrogen atom. The symbol M⁴denotes a transition metal of group 4 of the periodic table.]

The transition metal compound of an eighth aspect of the presentinvention is represented by the foregoing general formula (4), whereinthe three substituted cyclopentadienyl groups of (C₅H₃R³⁸R³⁹),(C₅H₃R⁴⁰R⁴¹) and (C₅H₃R⁴²R⁴³), are the same in structures.

The transition metal compound of a ninth aspect of the present inventionis represented by the following general formula (5).(C₉R⁴⁴R⁴⁵R⁴⁶R⁴⁷R⁴⁸R⁴⁹R⁵⁰)(C₉R⁵R⁵²R⁵³R⁵⁴R⁵⁵R⁵⁶R⁵⁷)—(C₉R⁵⁸R⁵⁹R⁶⁰R⁶¹R⁶²R⁶³R⁶⁴)M⁵H  Formula(5)[In the formula, (C₉R⁴⁴R⁴⁵R⁴⁶R⁴⁷R⁴⁸R⁴⁹R⁵⁰), (C₉R⁵¹R⁵²R⁵³R⁵⁴R⁵⁵R⁵⁶R⁵⁷)and (C₉R⁵⁸R59R⁶⁰R⁶¹R⁶²R⁶³R⁶⁴) denote an indenyl group or a substitutedindenyl group, respectively. The groups of R44 to R⁶⁴ are any one of ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or anorganosilicon group having a substituent of hydrocarbon having 1 to 30carbon atoms, which can be the same or different from one another. Anygroup of R⁴⁴ to R⁵⁰; R⁵¹ to R⁵⁷ and R⁵⁸ to R⁶⁴ may be bonded to oneanother forming a cyclic hydrocarbon group (including polycyclicstructure). At least one of R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴² and R⁴³ must be asubstituent other than hydrogen atom. The symbol M⁵ denotes a transitionmetal of group 4 of the periodic table.]

The transition metal compound of a tenth aspect of the present inventionis represented by the following general formula (6).(C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸)(C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²)(C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶)M⁶H  Formula (6)[In the formula, the groups of (C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸), (C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²)and (C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶) denote indenyl groups or substituted indenylgroups, respectively. R⁶⁵ to R⁷⁶ are any one of a hydrogen atom, ahydrocarbon group having 1 to 30 carbon atoms or an organosilicon grouphaving a substituent of hydrocarbon having 1 to 30 carbon atoms, whichmay be the same or different from one another. Among them, R⁶⁵ to R⁶⁸;R⁶⁹ to R⁷² and R⁷³ to R⁷⁶ can be bonded to the carbon atoms of4-position, 5-position, 6-position and 7-position (positions ofsix-membered ring) of the respective indenyl groups to form cyclichydrocarbon groups (including polycyclic structure). The symbol M⁶denotes a transition metal of group 4 of the periodic table.]

The transition metal compound of an eleventh aspect of the presentinvention is represented by the foregoing general formula (6), whereinthe three substituted indenyl groups of (C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸),(C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²) and (C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶), are the same in structure.

The transition metal compound of a twelfth aspect of the presentinvention is represented by any one of the foregoing general formulae(1) to (6), wherein the transition metal of group 4 of the periodictable is Zr.

The catalyst for use in olefin polymerization in the present inventionis composed of any one of the transition metal compounds described inthe foregoing first to twelfth aspects, an organoaluminum oxy compoundand/or a compound which can form an ion pair with the transition metalcompound.

The second catalyst for olefin polymerization in the present inventionis the one in which the above-mentioned organoaluminum oxy compound ismethyl aluminoxane.

The third catalyst for olefin polymerization in the present invention isa solid catalyst, which is prepared by supporting the foregoing catalyston a carrier.

The fourth catalyst for olefin polymerization in the present inventionis a solid catalyst, in which any one of the transition metal compoundsdescribed in the forgoing first to twelfth aspects is supported onlayered silicate.

The method for producing polyolefin of the present invention is apolymerizing method, in which olefin is polymerized in the presence ofany one of the catalyst for olefin polymerization as described above.

The second aspect of the method for producing polyolefin of the presentinvention is a polymerizing method, in which the foregoing olefinpolymerization is homopolymerization of ethylene or copolymerization ofethylene and α-olefin.

The transition metal compounds of the present invention will bedescribed in more detail.

In the transition metal compound in the general formula (1) of theinvention, each of C₅R¹R²R³R⁴R⁵, C₅R⁶R⁷R⁸R⁹R¹⁰ and C₅R¹¹R¹²R¹³R¹⁴R¹⁵denotes a cyclopentadienyl group or a substituted cyclopentadienylgroup. Each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴ and R¹⁵ is any one of a hydrogen atom, a hydrocarbon group having 1to 30 carbon atoms or an organosilicon group having a substituent ofhydrocarbon having 1 to 30 carbon atoms, which can be the same ordifferent from one another. The number of carbon atoms is preferably 1to 24, and more preferably 1 to18. Any of R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ can be bonded to one another toform a cyclic hydrocarbon group (including polycyclic structure),provided that at least one of R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ must be a substituent group other thanhydrogen atom.

The hydrocarbon groups of R¹, R², R³, R⁴, R⁵, R⁶, R⁷ R⁸ R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴ and R¹⁵ are exemplified by alkyl groups such as methylgroup, ethyl group, propyl group, butyl group, pentyl group, hexyl groupand cyclohexyl group; alkenyl groups such as vinyl group and allylgroup; aryl groups such as phenyl group, dimethylphenyl group,diethylphenyl group, dipropylphenyl group, dibutylphenyl group,trimethylphenyl group, triethylphenyl group, tripropylphenyl group,tributylphenyl group, biphenyl group, naphthyl group and anthryl group;and arylalkyl groups such as trityl group, phenethyl group, styrylgroup, benzhydryl group, phenylpropyl group, phenylbutyl and neophylgroup. These groups may be branched structure.

As more particular examples, there are methyl group, ethyl group, propylgroup, butyl group, cyclohexyl group, vinyl group, allyl group andphenyl group. Among these groups, methyl group, ethyl group, propylgroup, butyl group and phenyl group are more preferable.

The organosilicon groups having substituent of hydrocarbon with 1 to 30carbon atoms of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴ and R¹⁵ are exemplified by alkylsilyl groups having substituent ofalkyl group such as methyl group, ethyl group, propyl group, butylgroup, pentyl group, hexyl group and cyclohexyl group; alkenylsilylgroups having substituent of alkenyl group such as vinyl group and allylgroup; arylsilyl groups having substituent of aryl group such as phenylgroup, dimethylphenyl group, diethylphenyl group, dipropylphenyl group,dibutylphenyl group, trimethyl-phenyl group, triethylphenyl group,tripropylphenyl group, tributylphenyl group, biphenyl group, naphthylgroup and anthryl group; and arylalkylsilyl groups having substituent ofarylalkyl group such as trityl group, phenethyl group, styryl group,benzhydryl group, phenylpropyl group, phenylbutyl group and neophylgroup. These groups can have a branched chain.

They are exemplified more particularly by trimethylsilyl group,triethylsilyl group, tripropylsilyl group, tributylsilyl group,trivinylsilyl group, triallylsilyl group and triphenylsilyl group. Amongthem, trimethylsilyl group, triethylsilyl group and triphenylsilyl groupare more preferable.

The groups of R¹, R², R³, R⁴ and R⁵; or R⁶, R⁷, R⁸, R⁹ and R¹⁰; or R¹¹,R¹², R¹³, R¹⁴ and R¹⁵ can be bonded to one another, especially toadjacent group to form a cyclic hydrocarbon group (including polycyclicstructure).

(C₅R¹R²R³R⁴R⁵), (C₅R⁶R⁷R⁸R⁹R¹⁰) and (C₅R¹¹R¹²R¹³R¹⁴R¹⁵) as the cyclichydrocarbon groups (including polycyclic structure) that are formed bythe bonding are exemplified by indenyl group; alkylindenyl group havingone or more alkyl groups such as methyl group, ethyl group, propylgroup, butyl group, pentyl group, hexyl group or cyclohexyl group;alkenylindenyl group having one or more alkenyl group such as vinylgroup or allyl group; arylindenyl group having one or more aryl groupsuch as phenyl group, dimethylphenyl group, diethylphenyl group,dipropylphenyl group, dibutyl-phenyl group, trimethylphenyl group,triethylphenyl group, tripropylphenyl group, tributylphenyl group,biphenyl group, naphthyl group or anthryl group; arylalkylindenyl grouphaving one or more arylalkyl group such as trityl group, phenethylgroup, styryl group, benzhydryl group, phenylpropyl group, phenylbutylor neophyl group; tetrahydroindenyl group; benzoindenyl group havingpolycyclic structure, wherein the benzoindenyl group is the one havingthe structure represented by the following structural formula (1) or(2), and the same being applied to the description hereinafter;alkylbenzoindenyl groups having one or more alkyl group such as methylgroup, ethyl group, propyl group, butyl group, pentyl group, hexyl groupor cyclohexyl group; alkenylbenzoindenyl groups having one or morealkenyl group such as vinyl group or allyl group; arylbenzoindenylgroups having one or more of aryl group such as phenyl group,dimethylphenyl group, diethylphenyl group, dipropylphenyl group,dibutylphenyl group, trimethyl-phenyl group, triethylphenyl group,tripropylphenyl group, tributylphenyl group, biphenyl group, naphthylgroup or anthryl group; arylalkyl-benzoindenyl groups having one or morearylalkyl group such as trityl group, phenethyl group, styryl group,benzhydryl group, phenylpropyl group, phenylbutyl group or neophylgroup; dibenzoindenyl group having polycyclic structure, wherein thedibenzoindenyl group is the one having the structure represented by thefollowing. structural formula (3). The same is applied to thedescription hereinafter; alkyldibenzoindenyl groups having one or morealkyl group such as methyl group,- ethyl group, propyl group, butylgroup, pentyl group, hexyl group or cyclohexyl group;alkenyl-dibenzoindenyl groups having one or more alkenyl group such asvinyl group or allyl group; aryldibenzoindenyl groups having one or morearyl group such as phenyl group, dimethylphenyl group, diethylphenylgroup, dipropylphenyl group, dibutylphenyl group, trimethylphenyl group,triethylphenyl group, tripropylphenyl group, tributylphenyl group,biphenyl group, naphthyl group or anthryl group; arylalkyldibenzoindenylgroups having one or more arylalkyl group such as trityl group,phenethyl group, styryl group, benzhydryl group, phenylpropyl group,phenylbutyl group or neophyl group; azulenyl group; alkylazulenyl grouphaving one or more alkyl group such as methyl group, ethyl group, propylgroup, butyl group, pentyl group, hexyl group or cyclohexyl group;alkenylazulenyl groups having one or more alkenyl group such as vinylgroup or allyl group; arylazulenyl groups having one or more aryl groupsuch as phenyl group, dimethylphenyl group, diethylphenyl group,dipropylphenyl group, dibutylphenyl group, trimethylphenyl group,triethylphenyl group, tripropylphenyl group, tributylphenyl group,biphenyl group, naphthyl group or anthryl group; and arylalkylazulenylgroups having one or more arylalkyl group such as trityl group,phenethyl group, styryl group, benzhydryl group, phenylpropyl group,phenylbutyl group and neophyl group. These substituents can be branchedones.

The above groups are exemplified more particularly by indenyl group,methylindenyl group, ethylindenyl group, propylindenyl group,butylindenyl group,. vinylindenyl group, allylindenyl group,phenylindenyl group, tolylindenyl group, biphenylindenyl group,naphthylindenyl group, anthryl-indenyl group, benzylindenyl group,dimethyindenyl group, trimethylindenyl group, tetramethylindenyl group,diethylindenyl group, triethylihdenyl group, tetraethylindenyl group,dipropylindenyl group, tripropylindenyl group, tetrapropylindenyl group,dibutylindenyl group, tributylindenyl group, tetrabutylindenyl group,diphenylindenyl group, methylphenylindenyl group, methylnaphthylindlenylgroup, methylanthrylindenyl group, benzoindenyl group,methylbenzoindenyl group and dibenzoindenyl group.

Among them, preferable groups are exemplified by indenyl group,methylindenyl group, propylindenyl group, tetramethylindenyl group,tetraethylindenyl group, tetrapropylindenyl group, tetrabutylindenylgroup, phenylindenyl group, naphthylindenyl group, biphenylindenylgroup, benzo-indenyl group and dibenzoindenyl group. The indenyl group,tetramethyl-indenyl group, phenylindenyl group, benzoindenyl group anddibenzoindenyl group are more preferable.

The symbol M¹ denotes a transition metal of group 4 of the periodictable.

In the transition metal compounds of the present inventionas-represented by the foregoing general formula (2), each of(C₅R¹⁶R¹⁷R¹⁸R¹⁹R²⁰), (C₅R²¹R²²R²³R²⁴R²⁵) and (C5H₂R²⁶R²⁷R²⁸) denotes acyclopentadienyl group or a substituted cyclopentadienyl group, in whichthe structures of R¹⁶ to R²⁸ can be selected from similar structures ofR¹ to R¹⁵ as indicated in the description of the foregoing transitionmetal compounds of general formula (1). However, at least one of R¹⁶ toR²⁸ must be a substituent group other than hydrogen atom. Furthermore,the symbol M² denotes a transition metal of group 4 of the periodictable.

In the transition metal compounds of the general formula (2) in thepresent invention, the substituent groups of R²⁶, R²⁷ and R²⁸ in thesubstituted cyclopentadienyl group of (C₅R²⁶R²⁷R²⁸) are preferablybonded to their adjacent carbon atoms of 1-position, 2-position and3-position of the cyclopentadienyl group.

In the transition metal compounds of the general formula (3) in thepresent invention, (C₅H₂R²⁹R³⁰R³¹), (C₅H₂R³²R³³R³⁴) and (C₅H₂R³⁵R³⁶ R³⁷)denote cyclopentadienyl groups or substituted cyclopentadienyl groups,respectively. The substituent groups of R²⁹ to R³⁷ can be selected fromsimilar structures of R¹ to R¹⁵ in the description of the foregoingtransition metal compounds of the general formula (1). However, at leastone of R²⁹ to R³⁷ must be a substituent group other than hydrogen atom.The symbol M³ denotes a transition metal of group 4 of the periodictable.

In the transition metal compound of the general formula (3), thesubstituent groups of R²⁹, R³⁰ and R³¹; R³², R³³ and R³⁴; or R³⁵, R³⁶and R³⁷; of the cyclopentadienyl groups are preferably bonded to theiradjacent carbon atom of 1-position, 2-position and 3-position of thecyclopentadienyl group. It is more preferable that the three substitutedcyclopentadienyl groups of (C₅H₂R²⁹R³⁰R³¹), (C₅H₂R³²R³³R³⁴) and(C₅H₂R³⁵R³⁶R³⁷), are of the same structure.

In the transition metal compounds of the general formula (4) of thepresent invention, (C₅H₃R³⁸R³⁹), (C₅H₃R⁴⁰R⁴¹) and (C₅H₃R⁴²R⁴³) denotecyclopentadienyl groups or substituted cyclopentadienyl groups,respectively. R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴² and R⁴³ denote substituent groupsof the cyclopentadienyl group or substituted cyclopentadienyl group. R³⁸to R⁴³ can be selected from similar structures of R¹ to R¹⁵ in thedescription of the foregoing transition metal compounds of the generalformula (1). At least one of R³⁸ to R⁴³ must be a substituent other thanhydrogen atom. The symbol M⁴ denotes a transition metal of group 4 ofthe periodic table.

In the transition metal compounds of the general formula (4) of thepresent invention, it is preferable that the three substitutedcyclopentadienyl groups of (C₅H₃R³⁸R³⁹), (C₅H₃R⁴⁰R⁴¹) and (C₅H₃R⁴²R⁴³)are the same.

In the transition metal compound of the general formula (5) of thepresent invention, (C₉R⁴⁴R⁴⁵R⁴⁶R⁴⁷R⁴⁸R⁴⁹R⁵⁰), (C₉R⁵¹R⁵²R⁵³R⁵⁴R⁵⁵R⁵⁶R⁵⁷)and (C₉R⁵⁸R⁵⁹R⁶⁰R⁶¹R⁶²R⁶³R⁶⁴) denote indenyl groups or substitutedindenyl groups, respectively. R⁴⁴ to R⁶⁴ are any one of hydrogen atom, ahydrocarbon group having 1 to 30 carbon atoms or an organosilicon grouphaving a substituent of hydrocarbon having 1 to 30 carbon atoms, whichmay be the same or different from one another. However, the number ofcarbon atoms is preferably 1 to 24, and more preferably 1 to 18. Thehydrocarbon groups of R⁴⁴ to R⁶⁴ are exemplified by alkyl groups such asmethyl group, ethyl group, propyl group, butyl group, pentyl group,hexyl group or cyclohexyl group; alkenyl groups such as vinyl group orallyl group; aryl groups such as phenyl group, dimethylphenyl group,diethylphenyl group, dipropylphenyl group, dibutylphenyl group,trimethylphenyl group, triethylphenyl group, tripropyl-phenyl group,tributylphenyl group, biphenyl group, naphthyl group or anthryl group;and arylalkyl groups such as trityl group, phenethyl group, styrylgroup, benzhydryl group, phenylpropyl group, phenylbutyl group orneophyl group. These groups can be branched ones.

They are more particularly exemplified by methyl group, ethyl group,propyl group, butyl group, cyclohexyl group, vinyl group, allyl groupand phenyl group. Above all, methyl group, ethyl group, propyl group,butyl group and phenyl group are more preferable.

The organosilicon groups having substituent of hydrocarbon with 1 to 30carbon atoms of R⁴⁴ to R⁶⁴ are exemplified by alkylsilyl groups havingsubstituent of alkyl group such as methyl group, ethyl group, propylgroup, butyl group, pentyl group, hexyl group or cyclohexyl group;alkenylsilyl groups having substituent of alkenyl group such as vinylgroup or allyl group; arylsilyl groups having substituent of aryl groupsuch as phenyl group, dimethylphenyl group, diethylphenyl group,dipropylphenyl group, dibutyl-phenyl group, trimethylphenyl group,triethylphenyl group, tripropylphenyl group, tributylphenyl group,biphenyl group, naphthyl group or anthryl group; and arylalkylsilylgroups having substituent of arylalkyl group such as trityl group,phenethyl group, styryl group, benzhydryl group, phenylpropyl group,phenylbutyl group or neophyl group. These groups can be branched ones.

More particularly, they are exemplified by trimethylsilyl group,triethylsilyl group, tripropylsilyl group, tributylsilyl group,trivinylsilyl group, triallylsilyl group and triphenylsilyl group. Amongthem, trimethylsilyl group, triethylsilyl group and triphenylsilyl groupare more preferable.

In the groups of R⁴⁴ to R⁵⁰ or R⁵¹ to R⁵⁷ or R⁵⁸ to R⁶⁴, they can bebonded to one another forming a cyclic hydrocarbon group (includingpolycyclic structure).

The cyclic hydrocarbon groups (including polycyclic structure) that isformed through the bonding are exemplified by benzoindenyl group;alkylbenzoindenyl groups having one or more alkyl group such as methylgroup, ethyl group, propyl group, butyl group, pentyl group, hexyl groupor cyclohexyl group; alkenylbenzoindenyl groups having one or morealkenyl group such as vinyl group or allyl group; arylbenzoindenylgroups having one or more aryl group such as phenyl group,dimethylphenyl group, diethylphenyl group, dipropylphenyl group,dibutylphenyl group, trimethylphenyl group, triethylphenyl group,tripropylphenyl group, tributylphenyl group, biphenyl group, naphthylgroup or anthryl group; arylalkylbenzoindenyl groups having one or morearylalkyl group such as trityl group, phenethyl group, styryl group,benzhydryl group, phenylpropyl group, phenylbutyl group or neophylgroup; dibenzoindenyl group; alkyldibenzoindenyl groups having one ormore alkyl group such as methyl group, ethyl group, propyl group, butylgroup, pentyl group, hexyl group or cyclohexyl group;alkenyldibenzoindenyl groups having one or more alkenyl group such asvinyl group or allyl group; aryldibenzoindenyl groups having one or morearyl group such as phenyl group, dimethylphenyl group, diethylphenylgroup, dipropylphenyl group, dibutylphenyl group, tri-methylphenylgroup, triethylphenyl group, tripropylphenyl group, tributylphenylgroup, biphenyl group, naphthyl group or anthryl group; andarylalkyldibenzoindenyl groups having one or more arylalkyl group suchas trityl group, phenethyl group, styryl group, benzhydryl group,phenylpropyl group, phenylbutyl group or neophyl group. These groups canbe branched ones.

More particularly, they are exemplified by benzoindenyl group,methylbenzoindenyl group, dimethylbenzoindenyl group, phenylbenzoindenylgroup, diphenylbenzoindenyl group, dibenzoindenyl group,methyldibenzo-indenyl group and dimethyldibenzoindenyl group.

Among them, benzoindenyl group and dibenzoindenyl group are morepreferable.

The symbol M⁵ denotes a transition metal of group 4 of the periodictable.

In the transition metal compound of the general formula (6) of thepresent invention, the groups of (C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸), (C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²)and (C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶) denote indenyl groups or substituted indenylgroups, respectively.. The R⁶⁵ to R⁷⁶ can be selected from similarstructure ones as R⁴⁴ to R⁶⁴ that were described in the foregoingtransition metal compounds of the general formula (5). The symbol M⁶denotes a transition metal of group 4 of the periodic table. The groupsof R⁶⁵ to R⁶⁸; and R⁶⁹ to R⁷²; and R⁷³ to R⁷⁶ are bonded to carbon atomsof 4-position, 5-position, 6-position and 7-position (positions in thesix-membered ring) of the respective indenyl group and they can bebonded to one another forming a cyclic hydrocarbon group (includingpolycyclic structure).

In the structure of the transition metal compound of the general formula(6), it is preferable that the three substituted indenyl groups of(C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸), (C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²) and (C₉C₃R⁷³R⁷⁴R⁷⁵R⁷⁶) are thesame in structure.

As the transition metals of group 4 of the periodic table in thetransition metal compounds, Ti, Zr and Hf are exemplified. Among them,Ti and Zr are preferable, and Zr is more preferable.

In the following, examples of the transition metal compounds of thepresent invention are indicated. While, the invention is not limited tothese examples.

Cp₂(MeCp)ZrH, Cp₂(EtCp)ZrH, Cp₂(PrCp)ZrH, Cp₂(BuCp)ZrH, Cp₂(PhCp)ZrH,Cp₂(Me₂Cp)ZrH, Cp₂(MeEtCp)ZrH, Cp₂(MePrCp)ZrH, Cp₂(MeBuCp)ZrH,Cp₂(MePhCp)ZrH, Cp₂(Et₂Cp)ZrH, Cp₂(Me₃SiCp)ZrH, Cp₂(Et₃SiCp)ZrH,Cp₂(Ph₃SiCp)ZrH, Cp₂((Me₃Si)₂Cp)ZrH, Cp₂(Me₃Cp)ZrH, Cp₂(Et₃Cp)ZrH,Cp₂(Pr₃Cp)ZrH, Cp₂(Bu₃Cp)ZrH, Cp₂(Me₄Cp)ZrH, Cp₂(Et₄Cp)ZrH,Cp₂(Pr₄Cp)ZrH, Cp₂(Bu₄Cp)ZrH, Cp₂(Me₅Cp)ZrH, (MeCp)₂(Cp)ZrH,(MeCp)₂(EtCp)ZrH, (MeCp)₂(PrCp)ZrH, (MeCp)₂(BuCp)ZrH, (MeCp)₂(PhCp)ZrH,(MeCp)₂(Me₂Cp)ZrH, (MeCp)₂(MeEtCp)ZrH, (MeCp)₂(MePrCp)ZrH,(MeCp)₂(MeBuCp)ZrH, (MeCp)₂(MePhCp)ZrH, (MeCp)₂(Et₂Cp)ZrH,(MeCp)₂(Me₃SiCp)ZrH, (MeCp)₂(Et₃SiCp)ZrH, (MeCp)₂(Ph₃SiCp)ZrH,(MeCp)₂((Me₃Si)₂Cp)ZrH, (MeCp)₂(Me₃Cp)ZrH, (MeCp)₂(Et₃Cp)ZrH,(MeCp)₂(Pr₃Cp)ZrH, (MeCp)₂(Bu₃Cp)ZrH, (MeCp)₂(Me₄Cp)ZrH,(MeCp)₂(Et₄Cp)ZrH, (MeCp)₂(Pr₄Cp)ZrH, (MeCp)₂(Bu₄Cp)ZrH,(MeCp)₂(Me₅Cp)ZrH, (BuCp)₂(Cp)ZrH, (BuCp)₂(MeCp)ZrH, (BuCp)₂(EtCp)ZrH,(BuCp)₂(PrCp)ZrH, (BuCp)₂(PhCp)ZrH, (BuCp)₂(Me₂Cp)ZrH,(BuCp)₂(MeEtCp)ZrH, (BuCp)₂(MePrCp)ZrH, (BuCp)₂(MeBuCp)ZrH,(BuCp)₂(MePhCp)ZrH, (BuCp)₂(Et₂Cp)ZrH, (BuCp)₂(Me₃SiCp)ZrH,(BuCp)₂(Et₃SiCp)ZrH, (BuCp)₂(Ph₃SiCp)ZrH, (BuCp)₂((Me₃Si)₂Cp)ZrH,(BuCp)₂(Me₃Cp)ZrH, (BuCp)₂(Et₃Cp)ZrH, (BuCp)₂(Pr₃Cp)ZrH,(BuCp)₂(Bu₃Cp)ZrH, (BuCp)₂(Me₄Cp)ZrH, (BuCp)₂(Et₄Cp)ZrH,(BuCp)₂(Pr₄Cp)ZrH, (BuCp)₂(Bu₄Cp)ZrH, (BuCp)₂(Me₅Cp)ZrH,(Me₃SiCp)₂(Cp)ZrH, (Me₃SiCp)₂(MeCp)ZrH, (Me₃SiCp)₂(EtCp)ZrH,(Me₃SiCp)₂(PrCp)ZrH, (Me₃SiCp)₂(BuCp)ZrH, (Me₃SiCp)₂(PhCp)ZrH,(Me₃SiCp)₂(Me₂Cp)ZrH, (Me₃SiCp)₂(MeEtCp)ZrH, (Me₃SiCp)₂(MePrCp)ZrH,(Me₃SiCp)₂(MeBuCp)ZrH, (Me₃SiCp)₂(MePhCp)ZrH, (Me₃SiCp)₂(Et₂Cp)ZrH,(Me₃SiCp)₂(Et₃SiCp)ZrH, Me₃SiCp)₂(Ph₃SiCp)ZrH,(Me₃SiCp)₂((Me₃Si)₂Cp)ZrH, (Me₃SiCp)₂(Me₃Cp)ZrH, (Me₃SiCp)₂(Et₃Cp)ZrH,(Me₃SiCp)₂(Pr₃Cp)ZrH, (Me₃SiCp)₂(Bu₃Cp)ZrH, (Me₃SiCp)₂(Me₄Cp)ZrH,(Me₃SiCp)₂(Et₄Cp)ZrH, (Me₃SiCp)₂(Pr₄Cp)ZrH, (Me₃SiCp)₂(Bu₄Cp)ZrH,(Me₃SiCp)₂(Me₅Cp)ZrH, (Me₂Cp)₂(Cp)ZrH, (Me₂Cp)₂(MeCp)ZrH,(Me₂Cp)₂(EtCp)ZrH, (Me₂Cp)₂(PrCp)ZrH, (Me₂Cp)₂(BuCp)ZrH,(Me₂Cp)₂(PhCp)ZrH, (Me₂Cp)₂(MeEtCp)ZrH, (Me₂Cp)₂(MePrCp)ZrH,(Me₂Cp)₂(MeBuCp)ZrH, (Me₂Cp)₂(MePhCp)ZrH, (Me₂Cp)₂(Et₂Cp)ZrH,(Me₂Cp)₂(Et₃SiCp)ZrH, (Me₂Cp)₂(Ph₃SiCp)ZrH, (Me₂Cp)₂((Me₃Si)₂Cp)ZrH,(Me₂Cp)₂(Me₃Cp)ZrH, (Me₂Cp)₂(Et₃Cp)ZrH, (Me₂Cp)₂(Pr₃Cp)ZrH,(Me₂Cp)₂(Bu₃Cp)ZrH, (Me₂Cp)₂(Me₄Cp)ZrH, (Me₂Cp)₂(Et₄Cp)ZrH,(Me₂Cp)₂(Pr₄Cp)ZrH, (Me₂Cp)₂(Bu₄Cp)ZrH, (Me₂Cp)₂(Me₅Cp)ZrH,(Me₃Cp)₂(Cp)ZrH, (Me₃Cp)₂(MeCp)ZrH, (Me₃Cp)₂(EtCp)ZrH,(Me₃Cp)₂(PrCp)ZrH, (Me₃Cp)₂(BuCp)ZrH, (Me₃Cp)₂(PhCp)ZrH,(Me₃Cp)₂(Me₂Cp)ZrH, (Me₃Cp)₂(MeEtCp)ZrH, (Me₃Cp)₂(MePrCp)ZrH,(Me₃Cp)₂(MeBuCp)ZrH, (Me₃Cp)₂(MePhCp)ZrH, (Me₃Cp)₂(Et₂Cp)ZrH,(Me₃Cp)₂(Et₃SiCp)ZrH, (Me₃Cp)₂(Ph₃SiCp)ZrH, (MesCp)₂((Me₃Si)₂Cp)ZrH,(Me₃Cp)₂(Et₃Cp)ZrH, (Me₃Cp)₂(Pr₃Cp)ZrH, (Me₃Cp)₂(Bu₃Cp)ZrH,(Me₃Cp)₂(Me₄Cp)ZrH, (Me₃Cp)₂(Et₄Cp)ZrH, (Me₃Cp)₂(Pr₄Cp)ZrH,(Me₃Cp)₂(Bu₄Cp)ZrH, (Me₃Cp)₂(Me₅Cp)ZrH, (MeCp)₃ZrH, (EtCp)₃ZrH,(PrCp)₃ZrH, (BuCp)₃ZrH, (PhCp)₃ZrH, (Me₃SiCp)₃ZrH, (Et₃SiCp)₃ZrH,(Ph₃SiCp)₃ZrH, (Me₂Cp)₃ZrH, (Et₂Cp)₃ZrH,. (Pr₂Cp)₃ZrH, (Bu₂Cp)₃ZrH,(Me₃Cp)₃ZrH, (Et₃Cp)₃ZrH, (Pr₃Cp)₃ZrH, (Bu₃Cp)₃ZrH, (Me₄Cp)₃ZrH,(Et₄Cp)₃ZrH, (Pr₄Cp)₃ZrH, (Bu₄Cp)₃ZrH, (Me₅Cp)₃ZrH, (Et₅Cp)₃ZrH,(Pr₅Cp)₃ZrH, (Bu₅Cp)₃ZrH, Ind₂(Cp)ZrH, Ind₂(MeCp)ZrH, Ind₂(EtCp)ZrH,Ind₂(PrCp)ZrH, Ind₂(BuCp)ZrH, Ind₂(PhCp)ZrH, Ind₂(Me₂Cp)ZrH,Ind₂(MeEtCp)ZrH, Ind₂(MePrCp)ZrH, Ind₂(MeBuCp)ZrH, Ind₂(MePhCp)ZrH,Ind₂(Et₂Cp)ZrH, Ind₂(Me₃SiCp)ZrH, Ind₂(Et₃SiCp)ZrH, Ind₂(Ph₃SiCp)ZrH,Ind₂((Me₃Si)₂Cp)ZrH, Ind₂(Me₃Cp)ZrH, Ind₂(Et₃Cp)ZrH, Ind₂(Pr₃Cp)ZrH,Ind₂(Bu₃Cp)ZrH, Ind₂(Me₄Cp)ZrH, Ind₂(Et₄Cp)ZrH, Ind₂(Pr₄Cp)ZrH,Ind₂(Bu₄Cp)ZrH, Ind₂(Me₅Cp)ZrH, (Cp)(Ind)(MeCp)ZrH, (Cp)(Ind)(EtCp)ZrH,(Cp)(Ind)(PrCp)ZrH, (Cp)(Ind)(BuCp)ZrH, (Cp)(Ind)(PhCp)ZrH,(Cp)(Ind)(Me₂Cp)ZrH, (Cp)(Ind)(MeEtCp)ZrH, (Cp)(Ind)(MePrCp)ZrH,(Cp)(Ind)(MeBuCp)ZrH, (Cp)(Ind)(MePhCp)ZrH, (Cp)(Ind)(Et₂Cp)ZrH,(Cp)(Ind)(Me₃SiCp)ZrH, (Cp)(Ind)(Et₃SiCp)ZrH, (Cp)(Ind)(Ph₃SiCp)ZrH,(Cp)(Ind)((Me₃Si)₂Cp)ZrH, (Cp)(Ind)(Me₃Cp)ZrH, (Cp)(Ind)(Et₃Cp)ZrH,(Cp)(Ind)(Pr₃Cp)ZrH, (Cp)(Ind)(Bu₃Cp)ZrH, (Cp)(Ind)(Me₄Cp)ZrH,(Cp)(Ind)(Et₄Cp)ZrH, (Cp)(Ind)(Pr₄Cp)ZrH, (Cp)(Ind)(Bu₄Cp)ZrH,(Cp)(Ind)(Me₅Cp)ZrH, MeInd₂(Cp)ZrH, MeInd₂(MeCp)ZrH, MeInd₂(EtCp)ZrH,MeInd₂(PrCp)ZrH, MeInd₂(BuCp)ZrH, MeInd₂(PhCp)ZrH, MeInd₂(Me₂Cp)ZrH,MeInd₂(MeEtCp)ZrH, MeInd₂(MePrCp)ZrH, MeInd₂(MeBuCp)ZrH,MeInd₂(MePhCp)ZrH, MeInd₂(Et₂Cp)ZrH, MeInd₂(Me₃SiCp)ZrH,MeInd₂(Et₃SiCp)ZrH, MeInd₂(Ph₃SiCp)ZrH, MeInd₂((Me₃Si)₂Cp)ZrH,MeInd₂(Me₃Cp)ZrH, MeInd₂(Et₃Cp)ZrH, MeInd₂(Pr₃Cp)ZrH, MeInd₂(Bu₃Cp)ZrH,MeInd₂(Me₄Cp)ZrH, MeInd₂(Et₄Cp)ZrH, MeInd₂(Pr₄Cp)ZrH, MeInd₂(Bu₄Cp)ZrH,MeInd₂(Me₅Cp)ZrH, (Cp)(MeInd)(MeCp)ZrH, (Cp)(MeInd)(EtCp)ZrH,(Cp)(MeInd)(PrCp)ZrH, (Cp)(MeInd)(BuCp)ZrH, (Cp)(MeInd)(PhCp)ZrH,(Cp)(MeInd)(Me₂Cp)ZrH, (Cp)(MeInd)(MeEtCp)ZrH, (Cp)(MeInd)(MePrCp)ZrH,(Cp)(MeInd)(MeBuCp)ZrH, (Cp)(MeInd)(MePhCp)ZrH, (Cp)(MeInd)(Et₂Cp)ZrH,(Cp)(MeInd)(Me₃SiCp)ZrH, (Cp)(MeInd)(Et₃SiCp)ZrH,(Cp)(MeInd)(Ph₃SiCp)ZrH, (Cp)(MeInd)((Me₃Si)₂Cp)ZrH,(Cp)(MeInd)(Me₃Cp)ZrH, (Cp)(MeInd)(Et₃Cp)ZrH, (Cp)(MeInd)(Pr₃Cp)ZrH,(Cp)(MeInd)(Bu₃Cp)ZrH, (Cp)(MeInd)(Me₄Cp)ZrH, (Cp)(MeInd)(Et₄Cp)ZrH,(Cp)(MeInd)(Pr₄Cp)ZrH, (Cp)(MeInd)(Bu₄Cp)ZrH, (Cp)(MeInd)(Me₅Cp)ZrH,PhInd₂(Cp)ZrH, PhInd₂(MeCp)ZrH, PhInd₂(EtCp)ZrH, PhInd₂(PrCp)ZrH,PhInd₂(BuCp)ZrH, PhInd₂(PhCp)ZrH, PhInd₂(Me₂Cp)ZrH, PhInd₂(MeEtCp)ZrH,PhInd₂(MePrCp)ZrH, PhInd₂(MeBuCp)ZrH, PhInd₂(MePhCp)ZrH,PhInd₂(Et₂Cp)ZrH, PhInd₂(Me₃SiCp)ZrH, PhInd₂(Et₃SiCp)ZrH,PhInd₂(Ph₃SiCp)ZrH, PhInd₂((Me₃Si)₂Cp)ZrH, PhInd₂(Me₃Cp)ZrH,PhInd₂(Et₃Cp)ZrH, PhInd₂(Pr₃Cp)ZrH, PhInd₂(Bu₃Cp)ZrH, PhInd₂(Me₄Cp)ZrH,PhInd₂(Et₄Cp)ZrH, PhInd₂(Pr₄Cp)ZrH, PhInd₂(Bu₄Cp)ZrH, PhInd₂(Me₅Cp)ZrH,(Cp)(PhInd)(MeCp)ZrH, (Cp)(PhInd)(EtCp)ZrH, (Cp)(PhInd)(PrCp)ZrH,(Cp)(PhInd)(BuCp)ZrH, (Cp)(PhInd)(PhCp)ZrH, (Cp)(PhInd)(Me₂Cp)ZrH,(Cp)(PhInd)(MeEtCp)ZrH, (Cp)(PhInd)(MePrCp)ZrH, (Cp)(PhInd)(MeBuCp)ZrH,(Cp)(PhInd)(MePhCp)ZrH, (Cp)(PhInd)(Et₂Cp)ZrH, (Cp)(PhInd)(Me₃SiCp)ZrH,(Cp)(PhInd)(Et₃SiCp)ZrH, (Cp)(PhInd)(Ph₃SiCp)ZrH,(Cp)(PhInd)((Me₃Si)₂Cp)ZrH, (Cp)(PhInd)(Me₃Cp)ZrH,(Cp)(PhInd)(Et₃Cp)ZrH, (Cp)(PhInd)(Pr₃Cp)ZrH, (Cp)(PhInd)(Bu₃Cp)ZrH,(Cp)(PhInd)(Me₄Cp)ZrH, (Cp)(PhInd)(Et₄Cp)ZrH, (Cp)(PhInd)(Pr₄Cp)ZrH,(Cp)(PhInd)(Bu₄Cp)ZrH, (Cp)(PhInd)(Me₅Cp)ZrH, Me₄Ind₂(Cp)ZrH,Me₄Ind₂(MeCp)ZrH, Me₄Ind₂(EtCp)ZrH, Me₄Ind₂(PrCp)ZrH, Me₄Ind₂(BuCp)ZrH,Me₄Ind₂(PhCp)ZrH, Me₄Ind₂(Me₂Cp)ZrH, Me₄Ind₂(MeEtCp)ZrH,Me₄Ind₂(MePrCp)ZrH, Me₄Ind₂(MeBuCp)ZrH, Me₄Ind₂(MePhCp)ZrH,Me₄Ind₂(Et₂Cp)ZrH, Me₄Ind₂(Me₃SiCp)ZrH, Me₄Ind₂(Et₃SiCp)ZrH,Me₄Ind₂(Ph₃SiCp)ZrH, Me₄Ind₂((Me₃Si)₂Cp)ZrH, Me₄Ind₂(Me₃Cp)ZrH,Me₄Ind₂(Et₃Cp)ZrH, Me₄Ind₂(Pr₃Cp)ZrH, Me₄Ind₂(Bu₃Cp)ZrH,Me₄Ind₂(Me₄Cp)ZrH, Me₄Ind₂(Et₄Cp)ZrH, Me₄Ind₂(Pr₄Cp)ZrH,Me₄Ind₂(Bu₄Cp)ZrH, Me₄Ind₂(Me₅Cp)ZrH, (Cp)(Me₄Ind)(MeCp)ZrH,(Cp)(Me₄Ind)(EtCp)ZrH, (Cp)(Me₄Ind)(PrCp)ZrH, (Cp)(Me₄Ind)(BuCp)ZrH,(Cp)(Me₄Ind)(PhCp)ZrH, (Cp)(Me₄Ind)(Me₂Cp)ZrH, (Cp)(Me₄Ind)(MeEtCp)ZrH,(Cp)(Me₄Ind)(MePrCp)ZrH, (Cp)(Me₄Ind)(MeBuCp)ZrH,(Cp)(Me₄Ind)(MePhCp)ZrH, (Cp)(Me₄Ind)(Et₂Cp)ZrH,(Cp)(Me₄Ind)(Me₃SiCp)ZrH, (Cp)(Me₄Ind)(Et₃SiCp)ZrH,(Cp)(Me₄Ind)(Ph₃SiCp)ZrH, (Cp)(Me₄Ind)((Me₃Si)₂Cp)ZrH,(Cp)(Me₄Ind)(Me₃Cp)ZrH, (Cp)(Me₄Ind)(Et₃Cp)ZrH, (Cp)(Me₄Ind)(Pr₃Cp)ZrH,(Cp)(Me₄Ind)(Bu₃Cp)ZrH, (Cp)(Me₄Ind)(Me₄Cp)ZrH, (Cp)(Me₄Ind)(Et₄Cp)ZrH,(Cp)(Me₄Ind)(Pr₄Cp)ZrH, (Cp)(Me₄Ind)(Bu₄Cp)ZrH, (Cp)(Me₄Ind)(Me₅Cp)ZrH,BenzInd₂(Cp)ZrH, BenzInd₂(MeCp)ZrH, BenzInd₂(EtCp)ZrH,BenzInd₂(PrCp)ZrH, BenzInd₂(BuCp)ZrH, BenzInd₂(PhCp)ZrH,BenzInd₂(Me₂Cp)ZrH, BenzInd₂(MeEtCp)ZrH, BenzInd₂(MePrCp)ZrH,BenzInd₂(MeBuCp)ZrH, BenzInd₂(MePhCp)ZrH, BenzInd₂(Et₂Cp)ZrH,BenzInd₂(Me₃SiCp)ZrH, BenzInd₂(Et₃SiCp)ZrH, BenzInd₂(Ph₃SiCp)ZrH,BenzInd₂((Me₃Si)₂Cp)ZrH, BenzInd₂(Me₃Cp)ZrH, BenzInd₂(Et₃Cp)ZrH,BenzInd₂(Pr₃Cp)ZrH, BenzInd₂(Bu₃Cp)ZrH, BenzInd₂(Me₄Cp)ZrH,BenzInd₂(Et₄Cp)ZrH, BenzInd₂(Pr₄Cp)ZrH, BenzInd₂(Bu₄Cp)ZrH,BenzInd₂(Me₅Cp)ZrH, (Cp)(BenzInd)(MeCp)ZrH, (Cp)(BenzInd)(EtCp)ZrH,(Cp)(BenzInd)(PrCp)ZrH, (Cp)(BenzInd)(BuCp)ZrH, (Cp)(BenzInd)(PhCp)ZrH,(Cp)(BenzInd)(Me₂Cp)ZrH, (Cp)(BenzInd)(MeEtCp)ZrH,(Cp)(BenzInd)(MePrCp)ZrH, (Cp)(BenzInd)(MeBuCp)ZrH,(Cp)(BenzInd)(MePhCp)ZrH, (Cp)(BenzInd)(Et₂Cp)ZrH,(Cp)(BenzInd)(Me₃SiCp)ZrH, (Cp)(BenzInd)(Et₃SiCp)ZrH,(Cp)(BenzInd)(Ph₃SiCp)ZrH, (Cp)(BenzInd)((Me₃Si)₂Cp)ZrH,(Cp)(BenzInd)(Me₃Cp)ZrH, (Cp)(BenzInd)(Et₃Cp)ZrH,(Cp)(BenzInd)(Pr₃Cp)ZrH, (Cp)(BenzInd)(Bu₃Cp)ZrH,(Cp)(BenzInd)(Me₄Cp)ZrH, (Cp)(BenzInd)(Et₄Cp)ZrH,(Cp)(BenzInd)(Pr₄Cp)ZrH, (Cp)(BenzInd)(Bu₄Cp)ZrH,(Cp)(BenzInd)(Me₅Cp)ZrH, DibenzoInd₂(Cp)ZrH, DibenzoInd₂(MeCp)ZrH,DibenzoInd₂(EtCp)ZrH, DibenzoInd₂(PrCp)ZrH, DibenzoInd₂(BuCp)ZrH,DibenzoInd₂(PhCp)ZrH, DibenzoInd₂(Me₂Cp)ZrH, DibenzoInd₂(MeEtCp)ZrH,DibenzoInd₂(MePrCp)ZrH, DibenzoInd₂(MeBuCp)ZrH, DibenzoInd₂(MePhCp)ZrH,DibenzoInd₂(Et₂Cp)ZrH, DibenzoInd₂(Me₃SiCp)ZrH, DibenzoInd₂(Et₃SiCp)ZrH,DibenzoInd₂(Ph₃SiCp)ZrH, DibenzoInd₂((Me₃Si)₂Cp)ZrH,DibenzoInd₂(Me₃Cp)ZrH, DibenzoInd₂(Et₃Cp)ZrH, DibenzoInd₂(Pr₃Cp)ZrH,DibenzoInd₂(Bu₃Cp)ZrH, DibenzoInd₂(Me₄Cp)ZrH, DibenzoInd₂(Et₄Cp)ZrH,DibenzoInd₂(Pr₄Cp)ZrH, DibenzoInd₂(Bu₄Cp)ZrH, DibenzoInd₂(Me₅Cp)ZrH,(Cp)(DibenzoInd)(MeCp)ZrH, (Cp)(DibenzoInd)(EtCp)ZrH,(Cp)(DibenzoInd)(PrCp)ZrH, (Cp)(DibenzoInd)(BuCp)ZrH,(Cp)(DibenzoInd)(PhCp)ZrH, (Cp)(DibenzoInd)(Me₂Cp)ZrH,(Cp)(DibenzoInd)(MeEtCp)ZrH, (Cp)(DibenzoInd)(MePrCp)ZrH,(Cp)(DibenzoInd)(MeBuCp)ZrH, (Cp)(DibenzoInd)(MePhCp)ZrH,(Cp)(DibenzoInd)(Et₂Cp)ZrH, (Cp)(DibenzoInd)(Me₃SiCp)ZrH,(Cp)(DibenzoInd)(Et₃SiCp)ZrH, (Cp)(DibenzoInd)(Ph₃SiCp)ZrH,(Cp)(DibenzoInd)((Me₃Si)₂Cp)ZrH, (Cp)(DibenzoInd)(Me₃Cp)ZrH,(Cp)(DibenzoInd)(Et₃Cp)ZrH, (Cp)(DibenzoInd)(Pr₃Cp)ZrH,(Cp)(DibenzoInd)(Bu₃Cp)ZrH, (Cp)(DibenzoInd)(Me₄Cp)ZrH,(Cp)(DibenzoInd)(Et₄Cp)ZrH, (Cp)(DibenzoInd)(Pr₄Cp)ZrH,(Cp)(DibenzoInd)(Bu₄Cp)ZrH, (Cp)(BenzInd)(Me₅Cp)ZrH, Ind₃ZrH,Ind₂(MeInd)ZrH, Ind₂(EtInd)ZrH, Ind₂(PrInd)ZrH, Ind₂(BuInd)ZrH,Ind₂(Me₃SiInd)ZrH, Ind₂(Me₂Ind)ZrH, Ind₂(Et₂Ind)ZrH, Ind₂(Pr₂Ind)ZrH,Ind₂(Bu₂Ind)ZrH, Ind₂(Me₄Ind)ZrH, Ind₂(Et₄Ind)ZrH, Ind₂(Pr₄Ind)ZrH,Ind₂(Bu₄Ind)ZrH, Ind₂(NaphInd)ZrH, Ind₂(BiPhInd)ZrH, (MeInd)₃ZrH,(EtInd)₃ZrH, (PrInd)₃ZrH, (BuInd)₃ZrH, (Me₃SiInd)₃ZrH, (PhInd)₃ZrH,(NaphInd)₃ZrH, (BiPhInd)₃ZrH, (Me₂Ind)₃ZrH, (Et₂Ind)₃ZrH, (Pr₂Ind)₃ZrH,(Bu₂Ind)₃ZrH, (Me₂Ind)₂(Ind)ZrH, (Et₂Ind)₂(Ind)ZrH, (Pr₂Ind)₂(Ind)ZrH,(Bu₂Ind)₂(Ind)ZrH, (Ph₂Ind)₂(Ind)ZrH, (Me₃Ind)₃ZrH, (Et₃Ind)₃ZrH,(Pr₃Ind)₃ZrH, (Bu₃Ind)₃ZrH, (Me₄Ind)₃ZrH, (Et₄Ind)₃ZrH, (Pr₄Ind)₃ZrH,(Bu₄Ind)₃ZrH, (BenzInd)₃ZrH, (BenzInd)₂(Ind)ZrH, (BenzInd)(Ind)₂ZrH,(DibenzoInd)₂(Ind)ZrH, (DibenzoInd)(Ind)₂ZrH, (DibenzoInd)₃ZrH,(BenzInd)₂(DibenzoInd)ZrH, (BenzInd)(DibenzoInd)₂ZrH, and(DibenzoInd)(BenzInd)(Ind)ZrH.

In the above list of compounds, the following abbreviations were usedfor the respective groups (the same is applied to the descriptionhereinafter). That is, Cp=cyclopentadienyl group,MeCp=methylcyclopentadienyl group, EtCp=ethylcyclopentadienyl group,PrCp=propylcyclopentadienyl group, BuCp=butylcyclopentadienyl group,PhCp=phenylcyclopentadienyl group, Me₂Cp=dimethylcyclopentadienyl group,MeEtCp=methylethylcyclopentadienyl group,MePrCp=methylpropylcyclopentadienyl group,MeBuCp=methylbutylcyclopentadienyl group,MePhCp=methylphenylcyclopentadienyl group, Et₂Cp=diethylcyclopentadienylgroup, Me₃SiCp=trimethylsilylcyclopentadienyl group,Et₃SiCp=triethylsilylcyclopentadienyl group,Ph₃SiCp=triphenylsilylcyclopentadienyl group,(Me₃Si)₂Cp=bistrimethylsilylcyclopentadienyl group,Me₃Cp=trimethylcyclopentadienyl group, Et₃Cp=triethylcyclopentadienylgroup, Pr₃Cp=tripropylcyclopentadienyl group,Bu₃Cp=tributylcyclopentadienyl group, Me₄Cp=tetramethylcyclopentadienylgroup, Et₄Cp=tetraethylcyclopentadienyl group,Pr₄Cp=tetrapropylcyclopentadienyl group,Bu₄Cp=tetrabutylcyclopentadienyl group,Me₅Cp=pentamethylcyclopentadienyl group, Ind=indenyl group,MeInd=methylindenyl group, EtInd=ethylindenyl group, PrInd=propylindenylgroup, BuInd=butylindenyl group, Me₃SiInd=trimethylsilylindenyl group,PhInd=phenylindenyl group, NaphInd=naphthylindenyl group,BiPhInd=biphenylindenyl group, Me₂Ind=dimethylindenyl group,Et₂Ind=diethylindenyl group, Pr₂Ind=dipropylindenyl group,Bu₂Ind=dibutylindenyl group, Me₃Ind=trimethylindenyl group,Et₃Ind=triethylindenyl group, Pr₃Ind=tripropylindenyl group,Bu₃Ind=tributylindenyl group, Me₄Ind=tetramethylindenyl group,Et₄Ind=tetraethylindenyl group, Pr₄Ind=tetrapropylindenyl group,Bu₄Ind=tetrabutylindenyl group, BenzInd=benzoindenyl group, andDiBenzoInd=dibenzoindenyl group.

It is also possible to use two or more of these compounds as thecomponents of catalyst for olefin polymerization.

Among them, preferable compounds as the components of catalyst forolefin polymerization are exemplified by: Cp₂(MeCp)ZrH, Cp₂(PrCp)ZrH,Cp₂(BuCp)ZrH, Cp₂(Me₂Cp)ZrH, Cp₂(MePrCp)ZrH, Cp₂(MeBuCp)ZrH,Cp₂(Me₃SiCp)ZrH, Cp₂(Me₃Cp)ZrH, (MeCp)₂(Cp)ZrH, (MeCp)₂(PrCp)ZrH,(MeCp)₂(BuCp)ZrH, (MeCp)₂(Me₂Cp)ZrH, (MeCp)₂(MePrCp)ZrH,(MeCp)₂(MeBuCp)ZrH, (MeCp)₂(Me₃SiCp)ZrH, (MeCp)₂(Me₃Cp)ZrH,(BuCp)₂(Cp)ZrH, (BuCp)₂(MeCp)ZrH, (BuCp)₂(PrCp)ZrH, (BuCp)₂(Me₂Cp)ZrH,(BuCP)₂(MePrCp)ZrH, (BuCp)₂(MeBuCp)ZrH, (BuCp)₂(Me₃SiCp)ZrH,(Me₃SiCp)₂(Cp)ZrH, (Me₃SiCp)₂(MeCp)ZrH, (Me₃SiCp)₂(PrCp)ZrH,(Me₃SiCp)₂(BuCp)ZrH, (Me₃SiCp)₂(Me₂Cp)ZrH, (Me₃SiCp)₂(MePrCp)ZrH,(Me₃SiCp)₂(MeBuCp)ZrH, (Me₃SiCp)₂(Me₃Cp)ZrH, (Me₂Cp)₂(Cp)ZrH,(Me₂Cp)2(MeCp)ZrH, (Me₂Cp)₂(PrCp)ZrH, (Me₂Cp)₂(BuCp)ZrH,(Me₂Cp)₂(MePrCp)ZrH, (Me₂Cp)₂(MeBuCp)ZrH, (Me₂CP)₂(Me₃Cp)ZrH,(Me₃Cp)₂(Cp)ZrH, (MeCp)₃ZrH, (EtCp)₃ZrH, (PrCp)₃ZrH, (BuCp)₃ZrH,(PhCp)₃ZrH, (Me₃SiCp)₃ZrH, (Et₃SiCp)₃ZrH, (Me₂Cp)₃ZrH, (Me₃Cp)₃ZrH,(Me₄Cp)₃ZrH, (Me₅Cp)₃ZrH, Ind₂(Cp)ZrH, Ind₂(MeCp)ZrH, Ind₂(PrCp)ZrH,Ind₂(BuCp)ZrH, Ind₂(Me₂Cp)ZrH, Ind₂(MePrCp)ZrH, Ind₂(MeBuCp)ZrH,Ind₂(Me₃SiCp)ZrH, Ind₂(Me₃Cp)ZrH, (Cp)(Ind)(MeCp)ZrH,(Cp)(Ind)(PrCp)ZrH, (Cp)(Ind)(BuCp)ZrH, (Cp)(Ind)(Me₂Cp)ZrH,(Cp)(Ind)(Me3SiCp)ZrH, (Cp) (Ind) (Me₃Cp)ZrH, MeInd₂(Cp)ZrH,MeInd₂(MeCp)ZrH, MeInd₂(PrCp)ZrH, MeInd₂(BuCp)ZrH, MeInd₂(Me₂Cp)ZrH,MeInd₂(Me₃SiCp)ZrH, MeInd₂(Me₃Cp)ZrH, (Cp)(MeInd)(MeCp)ZrH,(Cp)(MeInd)(PrCp)ZrH, (Cp)(MeInd)(BuCp)ZrH, (Cp)(MeInd)(Me₂Cp)ZrH,(Cp)(MeInd)(MePrCp)ZrH, (Cp)(MeInd)(MeBuCp)ZrH, (Cp)(MeInd)(Me₃SiCp)ZrH,(Cp)(MeInd)(Me₃Cp)ZrH, PhInd₂(Cp)ZrH, PhInd₂(MeCp)ZrH, PhInd₂(PrCp)ZrH,PhInd₂(BuCp)ZrH, PhInd₂(Me₂Cp)ZrH, PhInd₂(MePrCp)ZrH, PhInd₂(MeBuCp)ZrH,PhInd₂(Me₃SiCp)ZrH, PhInd₂(Me₃Cp)ZrH, (Cp)(PhInd)(MeCp)ZrH,(Cp)(PhInd)(PrCp)ZrH, (Cp)(PhInd)(BuCp)ZrH, (Cp)(PhInd)(Me₂Cp)ZrH,(Cp)(PhInd)(MePrCp)ZrH, (Cp)(PhInd)(MeBuCp)ZrH, (Cp)(PhInd)(Me₃SiCp)ZrH,(Cp)(PhInd)(Me₃Cp)ZrH, Me₄Ind₂(Cp)ZrH, Me₄Ind₂(MeCp)ZrH,Me₄Ind₂(PrCp)ZrH, Me₄Ind₂(BuCp)ZrH, Me₄Ind₂(Me₂Cp)ZrH,Me₄Ind₂(MePrCp)ZrH, Me₄Ind₂(MeBuCp)ZrH, Me₄Ind₂(Me₃SiCp)ZrH,Me₄Ind₂(Me₃Cp)ZrH, (Cp)(Me₄Ind)(MeCp)ZrH, (Cp)(Me₄Ind)(PrCp)ZrH,(Cp)(Me₄Ind)(BuCp)ZrH, (Cp)(Me₄Ind)(Me₂Cp)ZrH, (Cp)(Me₄Ind)(MePrCp)ZrH,(Cp)(Me₄Ind) (MeBuCp)ZrH, (Cp)(Me₄Ind)(Me₃SiCp)ZrH, (Cp)(Me₄Ind)(Me₃Cp)ZrH, BenzInd₂(Cp)ZrH, BenzInd₂(MeCp)ZrH,BenzInd₂(PrCp)ZrH, BenzInd₂(BuCp)ZrH, BenzInd₂(Me₂Cp)ZrH,BenzInd₂(MePrCp)ZrH, BenzInd₂(MeBuCp)ZrH, BenzInd₂(Me₃SiCp)ZrH,BenzInd₂(Me₃Cp)ZrH, (Cp)(BenzInd)(MeCp)ZrH, (Cp)(BenzInd)(PrCp)ZrH,(Cp)(BenzInd)(BuCp)ZrH, (Cp)(BenzInd)(Me₂Cp)ZrH,(Cp)(BenzInd)(MePrCp)ZrH, (Cp)(BenzInd)(MeBuCp)ZrH, (Cp)(BenzInd)(Me₃SiCp)ZrH, (Cp)(BenzInd)(Me₃Cp)ZrH, DibenzoInd₂(Cp)ZrH,DibenzoInd₂(MeCp)ZrH, DibenzoInd₂(PrCp)ZrH, DibenzoInd₂(BuCp)ZrH,DibenzoInd₂(Me₂Cp)ZrH, DibenzoInd₂(MePrCp)ZrH, DibenzoInd₂(MeBuCp)ZrH,DibenzoInd₂(Me₃SiCp)ZrH, DibenzoInd₂(Me₃Cp)ZrH,(Cp)(DibenzoInd)(MeCp)ZrH, (Cp)(DibenzoInd)(PrCp)ZrH, (Cp) (DibenzoInd)(BuCp)ZrH, (Cp) (DibenzoInd) (Me₂Cp)ZrH, (Cp)(DibenzoInd)(MePrCp)ZrH,(Cp)(DibenzoInd)(MeBuCp)ZrH, (Cp)(DibenzoInd)(Me₃SiCp)ZrH,(Cp)(DibenzoInd)(Me₃Cp)ZrH, Ind₃ZrH, Ind₂(MeInd)ZrH, Ind₂(EtInd)ZrH,Ind₂(PrInd)ZrH, Ind₂(BuInd)ZrH, Ind₂(Me₃SiInd)ZrH, Ind₂(Me₂Ind)ZrH,Ind₂(Et₂Ind)ZrH, Ind₂(Pr₂Ind)ZrH, Ind₂(Bu₂Ind)ZrH, Ind₂(Me₄Ind)ZrH,Ind₂(Et₄Ind)ZrH, Ind₂(Pr₄Ind)ZrH, Ind₂(Bu₄Ind)ZrH, Ind₂(NaphInd)ZrH,Ind₂(BiPhInd)ZrH, (MeInd)₃ZrH, (EtInd)₃ZrH, (PrInd)₃ZrH, (BuInd)₃ZrH,.(Me₃SiInd)₃ZrH, (PhInd)₃ZrH, (NaphInd)₃ZrH, (BiPhInd)₃ZrH,(Me2Ind)3ZrH, (Et2Ind)₃ZrH, (Pr2Ind)3ZrH, (Bu₂Ind)₃ZrH,(Me₂Ind)₂(Ind)ZrH, (Et₂Ind)₂(Ind)ZrH, (Pr₂Ind)₂(Ind)ZrH,(Bu₂Ind)₂(Ind)ZrH, (Ph₂Ind)₂(Ind)ZrH, (Me₃Ind)₃ZrH, (Et₃Ind)₃ZrH,(Pr₃Ind)₃ZrH, (Bu₃Ind)₃ZrH, (Me₄Ind)₃ZrH, (Et₄Ind)₃ZrH, (Pr₄Ind)₃ZrH,(Bu₄Ind)₃ZrH, (BenzInd)₃ZrH, (BenzInd)₂(Ind)ZrH, (DibenzoInd)₂(Ind)ZrH,and (DibenzoInd)3ZrH.

Among them, more preferable compounds as the components of catalyst forolefin polymerization are: Cp₂(MeCp)ZrH, Cp₂(PrCp)ZrH, Cp₂(BuCp)ZrH,Cp₂(Me₂Cp)ZrH, Cp₂(Me₃SiCp)ZrH, Cp₂(Me₃Cp)ZrH, (MeCp)₂(Cp)ZrH,(MeCp)₂(PrCp)ZrH, (MeCp)₂(BuCp)ZrH, (MeCp)₂(Me₂Cp)ZrH,(MeCp)₂(Me₃SiCp)ZrH, (BuCp)₂(Cp)ZrH, (BuCp)₂(MeCp)ZrH, (BuCp)₂(PrCp)ZrH,(BuCp)₂(Me₂Cp)ZrH, BuCp)₂(Me₃SiCp)ZrH, (Me₃SiCp)₂(Cp)ZrH,(Me₃SiCp)₂(MeCp)ZrH, (Me₃SiCp)₂(Me₂Cp)ZrH, (Me₃SiCp)₂(Me₃Cp)ZrH,(Me₂Cp)₂(Cp)ZrH, (Me₂Cp)₂(MeCp)ZrH, (Me₂Cp)₂(MePrCp)ZrH,(Me₂Cp)₂(MeBuCp)ZrH, (Me₂Cp)₂(Me₃Cp)ZrH, (Me₃Cp)₂(Cp)ZrH, (MeCp)₃ZrH,(PrCp)₃ZrH, (BuCp)₃ZrH, (Me₃SiCp)₃ZrH, (Me₂Cp)₃ZrH, (Me₃Cp)₃ZrH,Ind₂(Cp)ZrH, Ind₂(MeCp)ZrH, Ind₂(PrCp)ZrH, Ind₂(BuCp)ZrH,Ind₂(Me₂Cp)ZrH, Ind₂(MePrCp)ZrH, Ind₂(MeBuCp)ZrH, Ind₂(Me₃SiCp)ZrH,Ind₂(Me₃Cp)ZrH, BenzInd₂(Cp)ZrH, BenzInd₂(MeCp)ZrH, BenzInd₂(PrCp)ZrH,BenzInd₂(BuCp)ZrH, BenzInd₂(Me₂Cp)ZrH, BenzInd₂(MePrCp)ZrH,BenzInd₂(MeBuCp)ZrH, BenzInd₂(Me₃SiCp)ZrH, BenzInd₂(Me₃Cp)ZrH, Ind₃ZrH,Ind₂(Me₂Ind)ZrH, Ind₂(Et₂Ind)ZrH, Ind₂(Pr₂Ind)ZrH, Ind₂(Bu₂Ind)ZrH,Ind₂(Me₄Ind)ZrH, Ind₂(Et₄Ind)ZrH, Ind₂(Pr₄Ind)ZrH, Ind₂(Bu₄Ind)ZrH,Ind₂(NaphInd)ZrH, Ind₂(BiPhInd)ZrH, (PhInd)₃ZrH, (NaphInd)₃ZrH,(BiPhInd)₃ZrH, (Me₂Ind)₃ZrH, (Et₂Ind)₃ZrH, (Pr₂Ind)₃ZrH, (Bu₂Ind)₃ZrH,(Me₄Ind)₃ZrH, (Et₄Ind)₃ZrH, (Pr₄Ind)₃ZrH, (Bu₄Ind)₃ZrH, (BenzInd)₃ZrH,(BenzInd)₂(Ind)ZrH and (DibenzoInd)₃ZrH.

The examples of transition metal compounds of the present invention thatare represented by the foregoing general formula (5) are shown in thefollowing.

That is, Ind₃ZrH, Ind₂(MeInd)ZrH, Ind₂(EtInd)ZrH, Ind₂(PrInd)ZrH,Ind₂(BuInd)ZrH, Ind₂(Me₃SiInd)ZrH, Ind₂(Me₂Ind)ZrH, Ind₂(Et₂Ind)ZrH,Ind₂(Pr₂Ind)ZrH, Ind₂(Bu₂Ind)ZrH, Ind₂(Me₄Ind)ZrH, Ind₂(Et₄Ind)ZrH,Ind₂(Pr₄Ind)ZrH, Ind₂(Bu₄Ind)ZrH, Ind₂(NaphInd)ZrH, Ind₂(BiphInd)ZrH,(MeInd)₃ZrH, (EtInd)₃ZrH, (PrInd)₃ZrH, (BuInd)₃ZrH, (Me₃SiInd)₃ZrH,(PhInd)₃ZrH, (NaphInd)₃ZrH, (BiPhInd)₃ZrH, (Me₂Ind)₃ZrH, (Et₂Ind)₃ZrH,(Pr₂Ind)₃ZrH, (Bu₂Ind)₃ZrH, (Me₂Ind)₂(Ind)ZrH, (Et₂Ind)₂(Ind)ZrH,(Pr₂Ind)₂(Ind)ZrH, (Bu₂Ind)₂(Ind)ZrH, (Ph₂Ind)₂(Ind)ZrH, (Me₃Ind)₃ZrH,(Et₃Ind)₃ZrH, (Pr₃Ind)₃ZrH, (Bu₃Ind)₃ZrH, (Me₄Ind)₃ZrH, (Et₄Ind)₃ZrH,(Pr₄Ind)₃ZrH, (Bu₄Ind)₃ZrH, (BenzInd)₃ZrH, (BenzInd)₂(Ind)ZrH,(BenzInd)(Ind)₂ZrH, (DibenzoInd)₂(Ind)ZrH, (DibenzoInd)(Ind)₂ZrH,(DibenzoInd)₃ZrH, (BenzInd)₂(DibenzoInd)ZrH, (BenzInd)(DibenzoInd)₂ZrHand (DibenzoInd)(BenzInd)(Ind)ZrH.

The abbreviations for the groups in the above structural formulae arethe same as defined in the forgoing passage.

It is possible to use two or more of these compounds as the componentsof catalyst for olefin polymerization.

Among the above examples, preferable compounds as the components of thecatalyst for olefin polymerization are exemplified by: Ind₃ZrH,Ind₂(Me₂Ind)ZrH, Ind₂(Et₂Ind)ZrH, Ind₂(Pr₂Ind)ZrH, Ind₂(Bu₂Ind)ZrH,Ind₂(Me₄Ind)ZrH, Ind₂(Et₄Ind)ZrH, Ind₂(Pr₄Ind)ZrH, Ind₂(Bu₄Ind)ZrH,Ind₂(NaphInd)ZrH, Ind₂(BiPhInd)ZrH, (PhInd)₃ZrH, (NaphInd)₃ZrH,(BiPhInd)₃ZrH, (Me₂Ind)₃ZrH, (Et₂Ind)₃ZrH, (Pr₂Ind)₃ZrH, (Bu₂Ind)₃ZrH,(Me₄Ind)₃ZrH, (Et₄Ind)₃ZrH, (Pr₄Ind)₃ZrH, (Bu₄Ind)₃ZrH, (BenzInd)₃ZrH,(BenzInd)(Ind)₂ZrH, (DibenzoInd)₂(Ind)ZrH, (DibenzoInd)(Ind)₂ZrH,(DibenzoInd)₃ZrH, (BenzInd)₂(DibenzoInd)ZrH, (BenzInd)(DibenzoInd)₂ZrHand (DibenzoInd)(BenzInd)(Ind)ZrH.

Among the above examples, more preferable compounds as the components ofthe catalyst for olefin polymerization are: Ind₃ZrH, (MeCp)(Cp)₂ZrH,(Me₃SiCp)(Cp)₂ZrH, (Me₃SiCp)₃ZrH, (MeCp)₃ZrH, (1,3-Me₂Cp)₃ZrH,Ind(1,3-Me₂Cp)₂ZrH, (1-Me-3-PrCp)₃ZrH, (BenzInd)₃ZrH and(DibenzoInd)₃ZrH.

The exemplar processes for synthesizing novel transition metal compoundsaccording to the present invention are described in the following asSynthetic Methods 1 and 2. It should be noted, however, that the presentinvention is not limited to these methods.

<Synthetic Method 1>

-   1) Preparation by bringing the following compounds of a), b) and c)    into contact.    -   a) (C₅R⁷⁷R⁷⁸R⁷⁹R⁸⁰R⁸¹)(C₅R⁸²R⁸³R⁸⁴R⁸⁵R⁸⁶)M⁷X¹ ₂    -   b) C₅HR⁸⁷R⁸⁸R⁸⁹R⁹⁰R⁹¹    -   c) LiR⁹²

In the above formulae, C₅R⁷⁷R⁷⁸R⁷⁹R⁸⁰R⁸¹ and C₅R⁸²R⁸³R⁸⁴R⁸⁵R⁸⁶ denotecyclopentadienyl groups or substituted cyclopentadienyl groups,respectively, and C₅HR⁸⁷R⁸⁸R⁸⁹R⁹⁰R⁹¹ denotes cyclopentadiene orsubstituted cyclopentadiene. R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴,R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸R⁸⁹, R⁹⁰ and R⁹¹ are similar to the groups of R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ in the noveltransition metal compound of the present invention represented by theforegoing general formula (1). X¹ denotes fluorine, chlorine, bromine oriodine. Two (X¹)'s may be the same or different from each other. As X¹,chlorine and bromine are preferable, and chlorine is more desirable. R⁹²denotes an alkyl group such as ethyl group, propyl group, butyl group orhexyl group. These groups can be branched ones. n-Butyl group ispreferable one.

When compounds a), b) and c) are brought into contact together, it isordinarily carried out under the atmosphere of inert gas such asnitrogen or. argon and generally in the presence of an aromatichydrocarbon, liquid inert hydrocarbon or oxygen-containing hydrocarbonsolvent, with or without stirring. As the liquid inert hydrocarbons,aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzeneare used, and aliphatic or alicyclic hydrocarbons such as heptane,hexane, decane, dodecane and cyclohexane are used. As theoxygen-containing hydrocarbon solvents, diethyl ether andtertahydrofuran are used.

The order of contacting is not limited especially, however, thepractical contacting process is preferably carried out as follows, thatis, after bringing a compound a) into contact with a compound c), thecompound b) is brought into contact.

In the contacting process, all compounds may be subjected to reactionsimultaneously or they are brought into contact slowly or step by stepover a period of a certain time. Furthermore, contacting of compoundscan be carried out in plurality of processes.

The contacting of compound a) with compound c) is desirably carried outat temperatures in the range of −100 to 0° C., preferably at −80 to −40°C., and for a period of 5 minutes to 24 hours, preferably for 30 minutesto 3 hours. After that, the temperature is raised to −30 to 30° C.,preferably about 0 to 10° C., and a halogenated alkali metal such asLiCl generated in this step is removed by filtration. Subsequently,after the compound b) is brought into contact with them, the reactionproduct is stirred for a period of 5 minutes to 3 days, preferably for 1hour to 24 hours, at a temperature in the range of 0° C. to 150° C.,preferably in the range of 20° C. to 80° C. After the solvent is removedfrom the solution of reaction, it is rinsed with an aliphatichydrocarbon such as pentane or hexane to obtain the novel transitionmetal compound of the present invention.

It is also possible that, after compounds a), b) and c) are brought intoreaction and heated with stirring, LiCl is removed the reaction solutionby filtration from the liquid inert hydrocarbon solution of aromatichydrocarbon such as benzene, toluene, xylene or ethylbenzene, oraliphatic or alicyclic hydrocarbon such as heptane, hexane, decane,dodecane or cyclohexane. Furthermore, it is also possible that, afterthe removal of solvent from the reaction solution, LiCl is removed byrinsing with oxygen-containing hydrocarbon solvent such astetrahydrofuran.

The ratios of the compounds are such that, relative to 1 mol of compounda), 1 to 50 mol, preferably 2 to 8 mol, of compound b) is used andgenerally 2 mol of compound c) is used.

<Synthetic Method 2>

-   1) Preparation by bringing the following compound d) into contact    with the following compound e).    -   d) Ind₃ZrH    -   e) C₅HR⁹³R⁹⁴R⁹⁵R⁹⁶R⁹⁷

In the above formulae, C₅HR⁹³R⁹⁴R⁹⁵R⁹⁶R⁹⁷ denotes cyclopentadiene orsubstituted cyclopentadiene. R⁹³, R⁹⁴, R⁹⁵, R⁹⁶ and R⁹⁷ are similar toR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ ofthe novel transition metal compound of the present invention representedby the general formula (1).

When the compound d) is brought into contact with the compound e), theprocess is usually carried out under the atmosphere of inert gas such asnitrogen or argon in the presence of a solvent of aromatic hydrocarbon,liquid inert hydrocarbon or oxygen-containing hydrocarbon with orwithout stirring. As the aromatic hydrocarbon, benzene, toluene, xyleneor ethylbenzene is generally used, and as the inert liquid hydrocarbon,aliphatic or alicyclic hydrocarbon such as heptane, hexane, decane,dodecane or cyclohexane is generally used. As the oxygen-containinghydrocarbon solvent, diethyl ether or tertahydrofuran is used.

Contacting of the compound d) and compound e) is usually carried out ata temperature in the range of −80 to 150° C., preferably 0 to 50° C.,and for a time length of 1 minute to 3 hours, preferably for 10 minutesto 1 hour. After that, the reaction solution is heated to a temperaturein the range of 0 to 150° C., preferably about 20 to 110° C. andsubjected to stirring for 5 minutes to 3 days, preferably 1 hour to 24hours. The solvent is then removed from the reaction solution, and theresultant product is rinsed with an aliphatic hydrocarbon such aspentane or hexane, thereby obtaining the novel transition metal compoundof the present invention (1).

The ratio of the compound e) to be used may be 1 to 50 mol, preferably 2to 8 mol, for 1 mol of the compound d).

Ind₃ZrH of compound d) can be obtained by the foregoing Synthetic Method1.

The novel transition metal compound proposed by the present inventioncan be used as a catalyst for olefin polymerization by combining withthe following organoaluminum oxy compound, or with a compound that isreactive with the novel transition metal compound to generate ion pairs,or with the mixture of them.

The organoaluminum oxy compound has “Al—O—Al” bond in the molecule. Thenumber of the bonds is usually in the range of 1 to 100, preferably 1 to50. The organoaluminum oxy compound is generally produced through thereaction of organoaluminum compound with water. The reaction oforganoaluminum compound with water is carried out in an inerthydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbon, alicyclichydrocarbon and aromatic hydrocarbon, such as pentane, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene or xylene, can be used.Among them, an aliphatic hydrocarbon or an aromatic hydrocarbon ispreferable.

As the organoaluminum compound used for preparing the organoaluminum oxycompound, any of compounds represented by the following general formula(7) may be employed. Among them, trialkylaluminum compound is preferablyused.R⁹⁸ _(t)AlX² _(3-t)  Formula (7)(In the above formula, R⁹⁸ denotes a hydrocarbon group such as alkylgroup, alkenyl group, aryl group or aralkyl group, which has 1 to 18carbon atoms, preferably 1 to 12 carbon atoms. X² denotes hydrogen atomor halogen atom. The symbol t denotes an integer of 1≦t≦3.)

The alkyl group of the above trialkylaluminum compound may also be anyone of methyl group, ethyl group, propyl group, isopropyl group, butylgroup, isobutyl group, pentyl group, hexyl group, octyl group, decylgroup and dodecyl group. Among them, the methyl group is especiallypreferable.

The above organoaluminum compounds can also be used in a mixture of twoor more kinds.

The ratio of water to the organoaluminum compound (molar ratio ofwater/Al) in the reaction is preferably 0.25/1 to 1.2/1 and morepreferably 0.5/1 to 1/1. The reaction temperature is generally in therange of −70 to 100° C., preferably −20 to 20° C. The retention time ofthe reaction is generally selected from the range of 5 minutes to 24hours, preferably 10 minutes to 5 hours. As the water content in thereaction, it is also possible to use not only the mere water but alsothe crystal water contained in copper sulfate hydrate or aluminumsulfate hydrate. Furthermore, the water generated in the reaction systemcan also be available.

Among the above organoaluminum oxy compounds, those obtained from thereaction of alkylaluminum with water is preferable, which is generallycalled as aluminoxane. The methylaluminoxane (including thosesubstantially consisting of methylaluminoxane (MAO)) is more preferableas the organoaluminum oxy compound.

As the organoaluminum oxy compound, the above organoaluminum oxycompounds may be used in a combination of two or more kinds. The aboveorganoaluminum oxy compounds can be used as a solution that is dissolvedor dispersed in the above-mentioned inert hydrocarbon solvent.

The exemplar compounds to generate ion pairs by the reaction with thenovel transition metal compound are borane compounds and boratecompounds.

More particularly, the borane compounds are exemplified bytriphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane,tri(m-tolyl)borane, tris(o-fluorophenyl)borane,tris(p-fluorophenyl)borane, tris(m-fluorophenyl)-borane,tris(2,5-difluorophenyl)borane, tris(3,5-difluotrophenyl)borane,tris(4-trifluoromethylphenyl)borane,tris(3,5-ditrifluoromethylphenyl)borane,tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl)borane,tris(perfluoro-anthryl)borane and tris(perfluorobinaphthyl)borane.

Among these compounds, preferable compound are exemplified bytris(3,5-ditrifluoromethylphenyl)borane,tris(2,6-ditrifluoromethylphenyl)-borane, tris(pentafluorophenyl)borane,tris(perfluoronaphthyl)borane, tris-(perfluorobiphenyl)borane,tris(perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane. Morepreferable compounds are exemplified bytris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane.

Particular first examples of the borate compounds are represented by thefollowing general formula (8).[L¹-H]+[BR⁹⁹R¹⁰⁰X³X⁴]⁻  Formula (8)

In the formula, L¹ is a neutral Lewis base, H is hydrogen atom and[L¹-H] is a Brønsted acid such as ammonium, anilinium or phosphonium.The ammonium is exemplified by trialkyl-substituted ammonium such astrimethylammonium, triethylammonium, tripropylammonium, tributylammoniumor tri(n-butyl)ammonium, and dialkylammonium such asdi(n-propyl)ammonium or dicyclohexylammonium.

As the aniliniums, N,N-dialkyl anilinium such as N,N-dimethyl anilinium,N,N-diethyl anilinium and N,N-2,4,6-pentamethyl anilinium areexemplified. Furthermore, as the phosphoniums, triarylphosphonium andtrialkylarylphosphonium, such as triphenylphosphonium,tributylphosphonium, tri(methylphenyl)phosphonium andtri(dimethylphenyl)phosphonium are exemplified.

R⁹⁹ and R¹⁰⁰ are aromatic hydrocarbon groups or substituted aromatichydrocarbon groups each having 6 to 20, preferably 6 to 16, carbonatoms, which are the same or difference from each other. They can bebonded to each other through cross-linking groups. As preferablesubstituents of the substituted aromatic group, alkyl group representedby methyl group, ethyl group or propyl group, and halogen atom such asfluorine, chlorine, bromine or iodine are exemplified.

X³ and X⁴ are any one of hydride group, halide group, hydrocarbyl grouphaving 1 to 20 carbon atoms and substituted hydrocarbyl group having 1to 20 carbon atoms, in which one or more hydrogen atoms are replaced byhalogen atom or atoms.

The actual examples of the compound represented by foregoing generalformula (8) are tributylammoniumtetra(pentafluorophenyl)borate,tributylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tributylammoniumtetra(3,5-ditrifluoromethylphenyl)borate,tributylammoniumtetra(2,6-difluorophenyl)borate,tributylammoniumtetra(perfluoronaphthyl)borate,dimethylaniliniumtetra(pentafluoronaphthyl)borate,dimethylaniliniumtetra(2,6-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(2,6-difluorophenyl)borate,dimethylaniliniumtetra(perfluoronaphthyl)borate,triphenylphosphoniumtetra(pentafluorophenyl)borate,triphenylphosphoniumtetra(2,6-ditrifluoromethylphenyl)borate,triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate,triphenylphosphoniumtetra(2,6-ifluorophenyl)borate,triphenylphosphoniumtetra(perfluoronaphthyl)borate,trimethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,triethylammoniumtetra(pentafluorophenyl)borate,triethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,triethylammoniumtetra(perfluo-ronaphthyl)borate,tripropylammoniumtetra(pentafluorophenyl)borate,tripropylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tripropylammoniumtetra(perfluoronaphthyl)borate,di(1-propyl)ammoniumtetra(pentafluorophenyl)borate anddicyclohexylammoniumtetraphenylborate.

Examples of more preferable compounds among them aretributylammoniumtetra(pentafluorophenyl)borate,tributylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tributylammoniumtetra(3,5 -ditrifluoromethylphenyl)borate,tributylammoniumtetra(perfluoronaphthyl)borate,dimethylaniliniumtetra(pentafluorophenyl)borate,dimethylanilinumtetra(2,6-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate anddimethylaniliniumtetra(perfluoronaphthyl)borate.

The second examples of the borate compounds are represented by thefollowing general formula (9).[L²]+[BR¹⁰¹R¹⁰²X⁵X⁶]⁻  Formula (9)

The symbol L² in the above formula is exemplified by carbo-cation,methyl cation, ethyl cation, propyl cation, isopropyl cation, butylcation, isobutyl cation, tert-butyl cation, pentyl cation, tropeniumcation, benzyl cation, trityl cation, sodium cation and proton. Thedefinitions for R¹⁰¹, R¹⁰², X⁵ and X⁶ are the same as those for R⁹⁹,R¹⁰⁰, X³ and X⁴ in the above general formula (8).

Particular examples for the above compounds are trityltetraphenylborate,trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate,trityltetra(m-tolyl)-borate, trityltetra(o-fluorophenyl)borate,trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate,trityltetra(3,5-difluorophenyl)borate,trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,trityltetra(3,5-ditrifluoromethylphenyl)borate,trityltetra(perfluoronaphthyl)borate, tropeniumtetraphenylborate,tropeniumtetra(o-tolyl)borate, tropeniumtetra(p-tolyl)borate,tropeniumtetra(m-tolyl)borate, tropeniumtetra(o-fluorophenyl)borate,tropeniumtetra(p-fluorophenyl)borate,tropeniumtetra(m-fluorophenyl)borate,tropeniumtetra(3,5-difluorophenyl)borate,tropeniumtetra(pentafluorophenyl)borate,tropeniumtetra(2,6-ditrifluoromethylphenyl)borate,tropeniumtetra(3,5-ditrifluoromethylphenyl)borate,tropeniumtetra-(perfluoronaphthyl)borate, NaBPh₄, NaB(o—CH₃—Ph)₄,NaB(p—CH₃—Ph)₄, NaB(m—CH₃—Ph)₄, NaB(o—F—Ph)₄, NaB(p—F—Ph)₄,NaB(m—F—Ph)₄, NaB(3,5-F₂—Ph)₄, NaB(C₆F₅)₄, NaB(2,6-(CF₃)₂—Ph)₄,NaB(3,5-(CF₃)₂—Ph)₄, NaB(C₁₀F₇)₄, H⁺BPh₄ ⁻-2-diethyl ether,H⁺B(3,5-F₂—Ph)₄-2-diethyl ether, H⁺B(C₆F)₄ ⁻-2-diethyl ether,H⁺B(2,6-(CF₃)₂—Ph)₄-2-diethyl ether, H⁺B(3,5-(CF₃)₂—Ph)₄-2-diethyl etherand H⁺B(C₁₀H₇)₄-2-diethyl ether.

Examples of preferable compounds among them aretrityltetra-(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,trityltetra(3,5-ditrifluoromethylphenyl)borate,trityltetra(perfluoronaphthyl)-borate,tropeniumtetra(pentafluorophenyl)borate,tropeniumtetra(2,6-ditrifluoromethylphenyl)borate,tropeniumtetra(3,5-ditrifluoromethylphenyl)-borate,tropeniumtetra(perfluoronaphthyl)borate, NaB(C₆F₅)₄,NaB(2,6-(CF₃)₂—Ph)₄, NaB(3,5-(CF₃)₂—Ph)₄, NaB(C₁₀F₇)₄, H⁺B(C₆F₅)₄⁻-2-diethyl ether, H⁺B(2,6-(CF₃)₂—Ph)₄-2-diethyl ether,H⁺B(3,5-(CF₃)₂—Ph)₄-2-diethyl ether and H⁺B(C₁₀H₇)₄-2-diethyl-ether.

More preferable ones are trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,tropeniumtetra-(pentafluorophenyl)borate,tropeniumtetra(2,6-ditrifluoromethylphenyl)borate, NaB(C₆F₅)₄,NaB(2,6-(CF₃)₂—Ph)₄, H⁺B(2,6-(CF₃)₂—Ph)₄-2-diethyl ether,H⁺B(3,5-(CF₃)₂—Ph)₄-2-diethyl ether and H⁺B(C₁₀F₇)₄-2-diethyl ether.

The catalyst for olefin polymerization, which is composed of the noveltransition metal compound of present invention, the organoaluminum oxycompound and the compound being reactive with the novel transition metalcompound to generate ion pairs, or their mixture, can be used as a solidcatalyst by supporting the composition on a carrier.

As the carrier, an inorganic carrier, a granular polymeric carrier ortheir mixture can be used. As the inorganic carriers, metals, metallicoxides, metallic chlorides, metallic carbonates, carbonaceus substancesor their mixtures can be used.

The metals preferably used for the inorganic carrier are exemplified byiron, aluminum and nickel.

Single oxides or double oxides of the element of groups 1 to 14 of theperiodic table can be used as the metallic oxides. They are exemplifiedby various natural or synthetic single or double oxides such as SiO₂,Al₂O₃, MgO, CaO, B₂O₃, TiO₂, ZrO₂, Fe₂O₃, Al₂O₃—MgO, Al₂O₃—CaO,Al₂O₃-SiO₂, Al₂O₃—MgO—CaO, Al₂O₃—MgO—SiO₂, Al₂O₃—CuO, Al₂O₃—Fe₂O₃,Al₂O₃—NiO or SiO₂—MgO. Incidentally, these chemical formulae are notintended to indicate molecular structure but only indicate thecompositions of the usable compounds. It should be noted that thestructures and compositions of the metallic oxides in the presentinvention are not limited by the above description.

The metallic oxides used in the present invention are allowed to absorba small quantity of water or impurities without causing anydisadvantage.

It is preferable to use chloride of alkali metal or alkaline earth metalas the metallic chloride. For example, MgCl₂ and CaCl₂ are particularlypreferable.

As the metallic carbonates, the carbonate of alkali metal or carbonateof alkaline earth metal are preferably used. More particularly,magnesium carbonate, calcium carbonate and barium carbonate areexemplified.

As the carbonaceous substance, carbon black and activated carbon areexemplified. Although the above-mentioned inorganic carriers can beused, the foregoing metallic oxides, silica and alumina are preferable.

It is desirable that the inorganic carrier is used by adjusting theamount of hydroxyl group on the surface to 0.8 to 1.5 m-mol/g by bakingit in an atmosphere of air or an inert gas such as nitrogen or argon ata temperature generally in the range of 200 to 800° C., preferably 460to 600° C.

The properties of inorganic carrier are not especially limited, however,it is advisable to use an inorganic carrier having the properties ofaverage diameter of generally 5 to 200 μm, preferably 10 to 150 μm;specific surface area of 150 to 1000 m²/g, preferably 200 to 500 m²/g;micro-pore volume of 0.3 to 2.5 cm³/g, preferably 0.5 to 2.0 cm³/g; andapparent specific gravity of 0.20 to 0.50 g/cm³, preferably 0.25 to 0.45g/cm³.

Although the above-mentioned inorganic carrier can be used as it stands,it can also be used after pre-treatment to bring it into contact withorganoaluminum compound, such as trimethylaluminum, triethylaluminum,triisobutylaluminum, trihexylaluminum, tripropylaluminum,tributylaluminum, trioctylaluminum, tridecylaluminum ordiisobutylaluminum halide, or organoaluminum oxy compound containingAl—O—Al bonds.

In order to prepare the catalyst for olefin polymerization of thepresent invention, there is no limitation concerning the contactingmethod, in which the novel transition metal compound is brought intocontact with an organoaluminum oxy compound, a compound being reactivewith the novel transition metal compound to generate ion pairs or theirmixture, and with the carrier. It is, however, possible to employoptionally the following methods.

(I) The novel transition metal compound, organoaluminum oxy compound,the compound that is reactive with the novel transition metal compoundto generate ion pairs are brought into contact with one another, andsubsequently the reaction product is brought into contact with thecarrier.

(II) The novel transition metal compound and the carrier are broughtinto contact together, and subsequently the reaction product is broughtinto contact with organoaluminum oxy compound, the compound that isreactive with the novel transition metal compound to generate ion pairs.

(III) The organoaluminum oxy compound, the compound being reactive withthe novel transition metal compound to generate ion pairs are broughtinto contact with the carrier, and subsequently they are brought intocontact with the novel transition metal compound.

Among these processes, the above (I) and (III) are preferable. In anycontacting method, the respective reactants are usually brought intocontact together under an inert atmosphere such as nitrogen or argon, inthe presence of a liquid inert hydrocarbon such aromatic hydrocarbons(usually those having 6 to 12 carbon atoms) such as benzene, toluene,xylene and ethylbenzene, or aliphatic or alicyclic hydrocarbons (havingof 5 to 12 carbon atoms) such as heptane, hexane, decane, dodecane andcyclohexane, with or without stirring.

It is generally desirable to carry out this contacting at a temperaturein the range of −100° C. to 200° C., preferably −50° C. to 100° C., andfor a retention time of 10 minutes to 50 hours, preferably 1 to 24hours.

In the contacting process of the novel transition metal compound, theorganoaluminum oxy compound, the compound being reactive with the noveltransition metal compound to generate ion pairs, with the carrier, anyaromatic hydrocarbon solvent in which a certain component is soluble orslightly soluble and an aliphatic or alicyclic hydrocarbon solvent inwhich a certain component is insoluble or slightly soluble, can be used.

When the contacting of the respective components is carried outstepwise, just the solvent as used in the preceding step can be used asthe solvent in the subsequent step without removing it. When a solventof large dissolving power is used in the preceding step of contacting, apoor solvent of liquid inert hydrocarbon, in which a certain componentis difficultly soluble or in soluble (e.g., aliphatic hydrocarbon,alicyclic hydrocarbon or aromatic hydrocarbon such as pentane, hexane,decane, dodecane, cyclohexane, benzene, toluene or xylene) may be addedin the subsequent step, and after desired product is recovered as asolid substance, the desired product is subjected to the next contactingstep by using any of the above-mentioned inert hydrocarbon solvent.Otherwise, after desired product is recovered as a solid substance byremoving a part or all of the solvent of good dissolving power bydrying, the desired product is subjected to the subsequent contactingstep. In the present invention, the any component may be brought into aplurality of contacting processes.

As the ratio of the novel transition metal compound to theorgano-aluminum oxy compound, or the novel transition metal compound tothe compound being reactive with the transition metal compound togenerate ion pairs and carrier, the following range is desirable,although there is no limitation.

In the case that organoaluminum oxy compound is used, the ratio ofelements of aluminum of the organoaluminum oxy compound to thetransition metal (M) of the novel transition metal compound, (Al/M), isgenerally in the range of 1 to 100,000, preferably 5 to 1000, and morepreferably 50 to 200. In the case that the compound being reactive withthe novel transition metal compound to generate ion pairs is used, theratio of elements of boron to the transition metal of the noveltransition metal compound, (BIM), is generally selected from the rangeof 0.01 to 100 (by mol), preferably 0.1 to 50 (by mol), and morepreferably 0.2 to 10 (by mol).

The carrier of 1 g is used for 0.0001 to 5 mmol of the transition metalin the novel transition metal compound, preferably for 0.001 to 0.5mmol, and more preferably for 0.01 to 0.1 mmol.

The novel transition metal compound, the organoaluminum oxy compound,the compound that is reactive with the novel transition metal compoundto generate ion pairs and carrier are brought into contact through anyone of the above-mentioned processes of (I) to (III), and by the removalof solvent, the solid state catalyst compound for olefin polymerizationcan be obtained. The removal of solvent is carried out under atmosphericpressure or reduced pressure at a temperature in the range of 0 to 200°C., preferably at 20 to 150° C. for a reaction time of 1 minute to 50hours, more preferably for 10 minutes to 10 hours.

Furthermore, the catalyst compound for olefin polymerization can also beobtained by the following procedure.

(IV) The novel transition metal compound and the carrier are broughtinto contact together, and after the removal of solvent, solid catalystcomponents are obtained. The solid catalyst components are brought intocontact with the organoaluminum oxy compound and the compound that isreactive with the novel transition metal compound to generate ion pairs,under polymerizing condition.

(V) The organoaluminum oxy compound, the compound that is reactive withthe novel transition metal compound to generate ion pairs and thecarrier are brought into contact together, and after removal of solventsolid catalyst components are obtained. The solid catalyst componentsare used as the novel catalyst components under polymerizing conditions.

In the above contacting processes of (IV) and (V), the ratios ofcomponents, contacting conditions and conditions for removing solventmay be the same as the forgoing processes.

The novel transition metal compound can also be used as a catalyst bysupporting it on layered silicate.

The layered silicate is the compound having a crystal structure that iscomposed by laying crystal planes formed by ionic bonds into parallellayers to overlap one another by weak bonding force.

Although most layered silicates are obtained from natural resources asthe main components of clay minerals, they are not limited to thenatural products but they are available as artificial products.

Among them, smectite group minerals such as montmorillonite, sauconite,beidellite, nontronite, saponite, hectorite, stevensite, bentonite ortaeniolite, and vermiculite group and mica group are preferable.

The natural products often have no ion-exchange capacity and no swellingproperty. In such a case, it is preferable to subject them to thetreatment to impart ion-exchange capacity (or swelling property) inorder to convert them having good ion-exchange capacity (or swellingproperty). The particularly preferable treatment for such purpose is thefollowing chemical treatment. In the chemical treatment as employed arethe surface treatment to remove impurities on their surfaces and thetreatment to change crystal structure or chemical composition of thelayered silicate. More particularly, they are exemplified by (a) acidtreatment by using hydrochloric acid, sulfuric acid or the like; (b)alkali treatment by using NaOH, KOH, NH₃ or the like; (c) salt treatmentby using salts composed of a cation containing at least one memberselected from the group 2 to 14 of the periodic table and at least onemember of an anion selected from halogen and anion of inorganic acidorigin; and (iv) organic substance treatment by using alcoholhydrocarbon compound, formaldehyde, aniline or the like. Thesetreatments can be applied singly or in combination of two or more.

The properties of the above-mentioned layered silicate particles can beadjusted by means of milling, granulation, classification, fractionationand so forth, at any step of before, during or after the treatments. Anymethod can be applied at will as far as it meets the purpose of process.Particularly, examples of granulation among these methods are spraygranulation, roll granulation, compression granulation, stirringgranulation, briquetting granulation, compacting granulation, extrusiongranulation, fluidized bed granulation, emulsion granulation, andsubmerged granulation. More preferable methods among them areexemplified by spray granulation, roll granulation and compressiongranulation.

Although the above-mentioned layered silicate is used as it stands, theycan also be used in combination with an organoaluminum compound such astrimethylaluminum, triethylaluminum, triisobutylaluminum,tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum,tridecylaluminum or diisobutylaluminumhydride, and an organoaluminum oxycompound containing Al—O—Al bond.

In order to support the novel transition compound on the layeredsilicate, the transition metal compound and the layered silicate arebrought into contact with each other, otherwise the transition metalcompound, the organoaluminum compound and the layered silicate arebrought into contact together. There is no limitation concerning thecontacting method of the components, especially. For example, thefollowing processes are employed optionally.

(VI) After the contacting of the novel transition metal compound and theorganoaluminum compound, the obtained reaction product is brought intocontact with the layered silicate.

(VII) After the contacting of the novel transition metal compound andthe carrier, the obtained product is brought into contact with theorganoaluminum compound.

(VIII) After the contacting of the ogranoaluminum oxy compound and thecarrier, the obtained product is brought into contact with the noveltransition metal compound.

Among these contacting methods, (I) and (II) are especially preferable.In any contacting method, components are brought into contact in theatmosphere of an inert gas such as nitrogen or argon usually, and in thepresence of aromatic hydrocarbon (generally having 6 to 12 carbon atoms)such as benzene, toluene, xylene and ethyl benzene, otherwise in thepresence of an inert liquid hydrocarbon of aliphatic or alicyclichydrocarbon (generally having 5 to 12 carbon atoms) such as heptane,hexane, decane, dodecane or cyclohexane, with or without stirring.

There is no limitation concerning the ratios of the novel transitionmetal compound, organoaluminum compound and the carrier to be used.However, the following ratios are desirable.

The amount of the novel transition metal compound supported on 1 g ofthe layered silicate is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol,and more preferably 0.01 to 0.1 mmol.

In the case that organoaluminum compound is used, the amount ofsupported aluminum is 0.01 to 100 mol, preferably 0.1 to 50 mol, andmore preferably 0.2 to 10 mol.

In the process of the supporting and the removal of solvent, the sameconditions as those in the forgoing inorganic carrier can be applied.

The thus obtained catalyst for olefin polymerization can be used, ifnecessary, after pre-polymerization of monomer.

The above-mentioned catalyst for polymerization is used forhomopolymerization and copolymerization of olefins. These olefins hereinreferred to include α-olefins, cycloolefins, dienes, trienes, styreneanalogs and olefins containing polar groups.

Included in the α-olefins are compounds each having 2 to 12 carbonatoms, preferably 2 to 8 carbon atoms. More particularly, ethylene,propylene, 1-butene, 1-hexene and 4-methyl-1-pentene are exemplified. Bythe used of the catalyst components of the present invention, thecopolymerization of two or more α-olefins is carried out in addition tothe homopolymerization. The copolymerization is any one of alternatingcopolymerization, random copolymerization and block copolymerization.The copolymerization of α-olefins includes the reaction of ethylene withα-olefin having carbon atoms of 3 to 12, preferably 3 to 8, such asethylene with propylene, ethylene with 1-butene, ethylene with 1-hexeneand ethylene with 4-methyl-1-pentene, and the reaction of propylene withα-olefin having carbon atoms of 3 to 12, preferably 3 to 8, such aspropylene with 1-butene, propylene with 4-methyl-1-pentene, propylenewith 1-hexene and propylene with 1-octene. In the copolymerization ofethylene or propylene with other α-olefin, the amount of other α-olefincan be selected from the range of 90 mol % or less in total amount ofmonomers. However, in-the copolymerization with ethylene, the amount isgenerally selected from the range of 40 mol % or less, preferably 30 mol% or less, and more preferably 20 mol % or less. In the copolymerizationwith propylene, the amount of other α-olefin is selected from the rangeof 1 to 90 mol %, preferably 5 to 90 mol %, and more preferably 10 to 70mol %.

As the cycloolefins, the compounds having carbon atoms of 3 to 24,preferably 3 to 18, can be used in the present invention. Thecycloolefins are exemplified by cyclopropene, cyclobutene, cyclopentene,cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene,cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene,norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene,5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene,5,5,6-trimethyl-2-norbornene and ethylidenenorbornene. The cycloolefinis usually copolymerized with the above-mentioned α-olefin. Theircontents in the copolymer is in the range of 50 mol % or less, generally1 to 50 mol %, and preferably 2 to 50 mol %.

As the dienes and the trienes, the compounds having carbon atoms of 4 to24, preferably 4 to 18, can be used in the present invention. They areexemplified by butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene,1,13-tetradecadiene, 2,6-dimethyl-1,5-heptadiene,2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-octadiene and 1,5,9-decatriene.When chain diene or chain triene is used in the present invention, it isgenerally copolymerized with the above-mentioned α-olefin. The contentsof the chain diene and/or the chain triene in the copolymer is generallyin the range of 0.1 to 50 mol %, and preferably 0.2 to 10 mol %.

The styrene analogs usable in the present invention are styrene orstyrene derivatives. The styrene derivatives are exemplified byt-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene andN,N-diethyl-p-aminoethylstyrene.

The reaction of the polymerization is carried out by slurrypolymerization, solution polymerization or gas-phase polymerization inthe presence of the above-mentioned catalyst.. Among these methods, theslurry polymerization and the solution polymerization are preferable. Inthese polymerization processes, olefins are polymerized without thesubstantial existence of oxygen and water, and with or without thepresence of an inert hydrocarbon solvent that is selected from aliphatichydrocarbon such as isobutane, hexane or heptane; aromatic hydrocarbonsuch as benzene, toluene or xylene, and alicyclic hydrocarbon such ascyclohexane or methylcyclohexane. The conditions for the polymerizationare such that the temperature is in the range of 20 to 200° C.,preferably 50 to 100° C.; the pressure is in the range of normalpressure to 7 MPa, preferably normal pressure to 3 MPa; and the reactiontime is 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

The molecular weight of produced polymer can be adjusted to some extentby changing the conditions of polymerization temperature and molarratios of components of catalyst. However, it is more effective foradjusting the molecular weight to supply hydrogen into the reactionsystem.

Even when a component for removal of water, called as scavenger, issupplied to the reaction system, the polymerization can be carried outwithout causing any difficulty. Preferable compounds as the scavengerare exemplified by organoaluminum compound such as trimethylaluminum,triethylaluminum and triisobutylaluminum; the above-mentionedorganoaluminum oxy compounds, modified organoaluminum compounds havingbranched alkyl groups, organozinc compounds such as diethylzinc ordibutylzinc; organomagnesium compounds such as diethylmagnesium,dibutylmagnesium or ethylbutylmagnesium; and Grignard compounds such asethylmagnesiumchloride or butylmagnesiumchloride. Among these compounds,triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are morepreferable, and triethylaluminum is most preferable.

They can be used also without any obstacle in the multistagepolymerization of two or more stages, in which conditions of hydrogenconcentrations, amounts of monomers, pressures and temperatures aredifferent from one another.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a drawing of the structure of the compound synthesized inExample 1, which is obtained by the processing of an electronic computeron the data of X-ray diffractiometry.

FIG. 2 is also a drawing of the structure of the compound synthesized inExample 6, which is obtained by the processing of an electronic computeron the data of X-ray diffractiometry.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in more detail with reference toexamples in the following. However, the present invention is not limitedto these examples.

The properties of polymers obtained in examples and comparative exampleswere measured according to the following methods.

<Measurement of Melting Point by Differential Scanning Calorimeter(DSC)>

A melting point measuring apparatus of model: DSC 6200 R made by SeikoInstruments Inc. was used. A sample of 5 mg was maintained at 180° C.for 3 minutes, and then it was cooled to 0° C. at a rate of 10°C./minute. Subsequently, after maintaining the sample at 0° C. for 10minutes, the melting point of the sample was measured by heating it at arate of 10° C./minute.

<Measurement of Molecular Weight and Molecular Weight Distribution byGPC (Gel Permeation Chromatography)>

In order to measure molecular weight distribution, GPC apparatus ofAlliance GPC 2000 made by Waters Corp. with a column of Shodex HT-806Mwas used by using a solvent of 1,2,4-trichlorobenzene. The temperaturewas 140° C. and the flow rate of the solvent was 1.0 ml per minute.

<Melt Index (MI)>

MI was measured according to ASTM D 1238-57T with a load of 2.16 kg at190° C.

EXAMPLE 1

Under nitrogen atmosphere, 1 mmol (0.39 g) ofbisindenylzirconium-dichloride (Ind₂ZrCl₂) was suspended in 30 ml oftoluene in a 100 ml eggplant type flask. After cooling the contents to−78° C. with a freezing mixture (dry ice-ethanol), 2 mmol ofn-butyllithium (n-BuLi) was added. The flask containing the mixedsolution was taken out from the freezing mixture and the temperature wasallowed to rise slowly. Subsequently, at a temperature of about 0° C., 4mmol of indene was added. The temperature was further allowed to rise toroom temperature and the contents were subjected to reaction for 30minutes. After the reaction, the precipitated lithiumchloride (LiCl) wasfiltered off. The filtrate was subjected to reaction again at atemperature of 50° C. for 12 hours. Subsequently, the precipitategenerated in this reaction was rinsed with n-hexane, and Ind₃ZrH wasobtained in a yield of 64%. The structure of this compound wasdetermined by ¹H-NMR, ¹³C-NMR and X-ray diffractometer.

Representative peaks of NMR spectrum were:

¹H-NMR (THF-d₈, Me₄Si): δ 2.03 (t, 3H), 2.95 (s, 1H), 5.79 (br, 6H),6.97 (m, 6H), 7.34(m, 6H);

¹³C-NMR (THF-d₈, Me₄Si): δ 90.12, 115.77, 123.51, 124.37, 131.36

The structure of the compound obtained by Example 1 is shown in FIG. 1,which was obtained by the processing of an electronic computer on thedata of X-ray diffractiometry.

EXAMPLE 2

Under nitrogen atmosphere, 1 mmol (0.29 g) ofbiscyclopentadienyl-zirconiumdichloride (CP₂ZrCl₂) was dissolved into 30ml of toluene in a 100 ml eggplant type flask. After the solution wascooled to −78° C. with a freezing mixture (dry ice-ethanol), 2 mmol ofn-butyllithium (n-BuLi) was added. The flask containing the solutionmixture was taken out from the freezing mixture and the temperature wasallowed to rise slowly. At a temperature of about 0° C., 4 mmol ofmethylcyclopentadiene was added. The temperature of the mixture wasallowed to rise to room temperature and the contents were subjected toreaction for 30 minutes. After the reaction, precipitatedlithiumchloride (LiCl) was filtered off. The filtrate was subjected toreaction again at 50° C. for 12 hours. Subsequently, the precipitategenerated by this reaction was rinsed with n-hexane, and (MeCp)(Cp)₂ZrHwas obtained in a yield of 70%. The structure of the compound wasdetermined by ¹H-NMR and ¹³C-NMR.

Representative peaks of NMR spectrum were:

¹H-NMR (C₆D₆, Me₄Si): δ 2.17(s, 3H), 2.98(s, 1H), 4.79(t, 2H), 5.31(t,2H), 5.34(s, 10H);

¹³C-NMR(C₆D₆, Me₄Si): δ 16.38, 102.55, 105.43, 110.04, 118.50

EXAMPLE 3

Under nitrogen atmosphere, 1 mmol (0.29 g) ofbiscyclopentadienylzirconiumdichloride (Cp₂ZrCl₂) was dissolved into 30ml of toluene in a 100 ml eggplant type flask. After the solution wascooled to −78° C. with a freezing mixture (dry ice-ethanol), 2 mmol ofn-butyllithium (n-BuLi) was added. The flask containing the solutionmixture was taken out from the freezing mixture and allowed thetemperature to rise slowly. At a temperature of about 0° C., 4 mmol oftrimethylsilylcyclopentadiene was added. The temperature of the mixturewas allowed to rise to room temperature and the contents were subjectedto reaction for 30 minutes. After the reaction, the precipitatedlithiumchloride (LiCl) was filtered off. The filtrate was subjected toreaction again at a temperature of 80° C. for 3 hours. After the removalof solvent, precipitate generated in this reaction was rinsed withn-hexane and (Me₃SiCp)(Cp)₂ZrH was obtained in a yield of 87%. Thestructure of the compound was determined by ¹H-NMR.

Representative peaks of NMR spectrum were:

1H-NMR (C₆D₆, Me₄Si): δ 0.40 (s, 9H), 2.65 (s, 1H), 4.48 (t, 2H), 5.29(s, 10H), 5.67 (t, 2H)

EXAMPLE 4

Under nitrogen atmosphere, 1 mmol (0.44 g) oftrisindenylzirconiumhydride (Ind₃ZrH) obtained in Example 1 wassuspended in 30 ml of toluene in a 100 ml eggplant type flask. Then, 8mmol of trimethylsilylcyclopentadiene was added. After the mixture wassubjected to reaction at 80° C. for 3 hours, the solvent was removed andsolid precipitate was rinsed with n-hexane. Subsequently, (Me₃SiCp)₃ZrHwas obtained in a yield of 88%. The structure of the compound wasdetermined by ¹H-NMR and ¹³C-NMR.

Representative peaks of NMR spectrum were:

¹H-NMR (C₆D₆, Me₄Si): δ 3.35 (s, 1H), 4.83 (t, 6H), 5.86 (t, 6H);

¹³C-NMR (C₆D₆, Me₄Si): δ 106.28, 110.10, 116.08

EXAMPLE 5

Under nitrogen atmosphere, 1 mmol (0.44 g) oftrisindenylzirconiumhydride (Ind3ZrH) obtained in Example 1 wassuspended in 30 ml of toluene in a 100 ml eggplant type flask. And 8mmol of methylcyclopentadiene was added. After the mixture was subjectedto reaction at 80° C. for 3 hours, the solvent was removed and solidprecipitate was rinsed with n-hexane. Subsequently, (MeCp)₃ZrH wasobtained in a yield of 87%. The structure of the compound was determinedby ¹H-NMR and ¹³C-NMR.

Representative peaks of NMR spectrum were:

¹H-NMR (C₆D₆, Me₄Si): δ 2.68 (s, 9H), 3.25 (s, 1H), 4.85 (t, 6H), 5.40(t, 6H);

¹³C-NMR (C₆D₆, Me₄Si): δ 16.41, 103.19, 110.52, 119.16

EXAMPLE 6

Under nitrogen atmosphere, 1 mmol (0.44 g) oftrisindenyl-zirconiumhydride (Ind₃ZrH) obtained in Example 1 wassuspended in 30 ml of toluene in a 100 ml eggplant type flask. And 8mmol of 1,3-dimethyl-cyclopentadiene was added. After the mixture wassubjected to reaction at 80° C. for 3 hours, the solvent was removed andsolid precipitate was rinsed with n-hexane. Subsequently,(1,3-Me₂Cp)₃ZrH was obtained in a yield of 80%. The structure of thecompound was determined by ¹H-NMR and ¹³C-NMR.

Representative peaks of NMR spectrum were:

¹H-NMR (C₆D₆, Me₄Si): δ 2.25 (s, 18H), 3.48 (s, 1H), 4.60 (t, 3H), 4.93(d, 6H);

¹³C-NMR (C₆D₆, Me₄Si): δ 15.90, 108.41, 115.36, 118.00

The structure of the compound obtained in Example 6 is shown in FIG. 2,which was obtained by the processing of an electronic computer on thedata of X-ray diffractiometry

EXAMPLE 7

Under nitrogen atmosphere, 0.42 mmol (0.185 g) oftrisindenylzirconiumhydride (Ind₃ZrH) obtained in Example 1 wassuspended in 8.4ml of toluene in a 50 ml eggplant type flask. After 1.68mmol of 1,3-dimethylcyclopentadiene was added, the mixture was subjectedto reaction at 40° C. for 48 hours. Subsequently, Ind(1,3-Me₂Cp)₂ZrH wasobtained. The yield was determined by ¹H-NMR was 50%.

Representative peaks of NMR spectrum were.

¹H-NMR (C₆D₆, Me₄Si): δ 3.56 (s, 1H), 4.23 (t, 2H), 4.42 (t, 2H), 4.57(t, 2H)

EXAMPLE 8

Under nitrogen atmosphere, 2.9 mmol (1.27 g) oftrisindenylzirconiumhydride (Ind₃ZrH) obtained in Example 1 wassuspended in 30 ml of toluene in a 50 ml eggplant type flask. Then, 11.6mmol of 1-methyl-3-propylcyclopentadiene was added and subjected toreaction at 80° C. for 2 hours. The solvent was then removed and solidprecipitate was rinsed with n-hexane. Subsequently, (1-Me-3-PrCp)₃ZrHwas obtained in a yield of 90%.

The structure of the compound was determined by ¹H-NMR.

Representative peaks of NMR spectrum were:

¹H-NMR (C₆D₆, Me₄Si): δ 0.96 (t, 9H), 2.27 (t, 9H), 3.41 (s, 1H), 4.63(s, 3H), 4.90 (m, 3H), 4.96 (m, 3H)

EXAMPLE 9

Under nitrogen atmosphere, 0.31 mmol (0.14 g) oftrisindenylzirconiumhydride (Ind₃ZrH) obtained in Example 1 wassuspended in 5 ml of hexane in a 50 ml eggplant type flask. Then, 1.2mmol of benzoindene (BenzInd) was added and the mixture was subjected toreaction at 50° C. for 2 hours. After the solvent was removed, solidprecipitate was rinsed with n-hexane. Subsequently, (BenzInd)3ZrH wasobtained in a yield of 83%. The structure of the compound was determinedby ¹H-NMR.

Representative peaks of NMR spectrum were:

¹H-NMR (C₆D₆, Me₄Si): δ 3.30 (t, 3H), 3.85 (s, 1H), 5.80 (s, 3H), 5.97(s, 3H), 7.25 (t, 3H), 7.35 (t, 3H), 7.66 (d, 3H), 7.51(d, 3H)

EXAMPLE 10

Under nitrogen atmosphere, 21 ml of toluene solution containing 0.1 molof dibenzoindene per 1 liter of toluene was added to 0.64 mmol (0.28 g)of trisindenylzirconiumhydride (Ind₃ZrH) obtained in Example 1 to form asuspension in a 50 ml eggplant type flask. The suspension was subjectedto reaction at 80° C. for 30 minutes. (After the suspension turned intoa uniform solution by heating, solid precipitate was generated.) Afterfiltration and rinsing with n-pentane, 0.38 g of precipitate wascollected. The precipitate was decomposed with methanol and wassubjected to ¹H-NMR, as a result only dibenzoindene was confirmed. Inview of the amount of dibenzoindene formed by the decomposition, it wasunderstood that the solid substance obtained by the reaction was(DibenzoInd)₃ZrH. The yield was 81%.

EXAMPLE 11

The following polymerization was carried out using Ind₃ZrH obtained inExample 1 as a component of catalyst.

Into a 20 ml Schlenk tube that was purged with nitrogen gas, 5 ml oftoluene, 5.0 μmol of a compound of Ind₃ZrH and 5.0 mmol of toluenesolution containing MAO (2.6 mmol/ml) were added together at roomtemperature, and the mixture was stirred for 5 minutes.

Toluene of 100 ml was supplied into a 200 ml stainless steel autoclave,which was equipped with a stirrer and was replaced with nitrogen gas inadvance. Subsequently, 1.4 ml of the above-mentioned catalyst solutionwas added and heated to 80° C. with stirring. Then, ethylene was fedinto the autoclave to make the pressure 0.6 MPa so as to startpolymerization. The polymerization was continued for 5 minutes and wasthen stopped by feeding ethanol.

Polyethylene was obtained through the polymerization. The polymerizationactivity was 74 kg PE/(mmol Zr-MPa-h). The polyethylene had theproperties of 102,600 in Mw and 2.97 in Mw/Mn.

EXAMPLE 12

By using Ind₃ZrH obtained in Example 1 as catalyst, the followingpolymerization process was carried out.

A 100 ml flask was fed with 0:4 mmol of Ind₃ZrH obtained in Example 1under nitrogen atmosphere. Then, 15 ml of toluene was added to generatea toluene suspension. Subsequently, 40 mmol of a solution ofmethylaluminoxane (concentration of 2.6 mmol/ml (number of moles of Alatom) was added and the mixture was stirred at room temperature for 10minutes.

Into a 300 ml flask, 10 g of SiO₂ sintered at 400° C. for 5 hours andthe whole amount of the above-mentioned solution were added. The solventwas removed by nitrogen gas blowing and pressure reduction, a solid ofcatalyst component with fluidity was obtained.

A 2.7 lit. stainless steel autoclave, which was equipped with a stirrer,kept at 75° C. and replaced with nitrogen gas was used. Into thisautoclave was added 0.25 ml of hexane solution of triethylaluminum (0.5mmol/ml) and 130 mg of the above-mentioned solid catalyst. Thepolymerization was then carried out for two hours with adjusting themolar ratio of 1-butene/ethylene in gas phase to 0.12 and the totalpressure to 0.9 MPa with feeding every gas.

The polymerization activity was 1730 g/(g catalyst-MPa-h). The obtainedethylene copolymer had properties of 1.4 g/10 minutes in MI, 0.9248g/cm³ in density, 124,500 in Mw, 2.5 in Mw/Mn, 0.42 g/cm³ in bulkdensity and 118.1° C. in melting point.

EXAMPLE 13

By using a compound of (1,3-Me₂CP)₃ZrH obtained in Example 6, thepolymerization was carried out as follows.

Into a 20ml Schlenk tube purged with nitrogen gas, 5 ml of toluene, 5.0μmol of the compound of (1,3-Me₂CP)₃ZrH and 5.0 mmol of toluene solutioncontaining MAO (2.6 mmol/ml) were fed at room temperature, and themixture was stirred for 1 minute.

A 200 ml stainless steel autoclave equipped with a stirrer was replacedwith nitrogen gas and fed with 100 ml of toluene. Subsequently, 1.4 mlof the above-mentioned solution containing catalyst was added and it washeated to 80° C. with stirring. Ethylene was then fed into the autoclaveso as to keep the pressure of 0.6 MPa and to start polymerization. Thepolymerization was carried out for 5 minutes. The polymerization wasstopped by the feeding of ethanol.

Polyethylene was obtained by the polymerization. The polymerizationactivity was 60 kg PE/(mmol Zr—MPa—h).

EXAMPLE 14

By using the compound of (Me₂CP)₃ZrH obtained in Example 6,polymerization was carried out as follows.

Under nitrogen atmosphere, a 100 ml flask was fed with 0.2 mmol of(Me₂CP)₃ZrH obtained in Example 6, and with 15 ml of toluene to form atoluene suspension. Subsequently, 40 mmol of methylaluminoxane solutionof a concentration of 2.9 mmol/ml (moles of Al atom) was added and itwas stirred at room temperature for 10 minutes.

A 300 ml flask was fed with 10 g of SiO₂ that was sintered at 650° C.for 5 hours, and the whole amount of the above-mentioned solution wasadded. The solvent was removed by nitrogen gas blowing and by reducedpressure, a fluidizable solid of catalyst component was obtained.

A 2.7 lit. stainless steel autoclave equipped with a stirrer wasreplaced with nitrogen gas and maintained at 75° C., and it was fed with0.3 ml of hexane solution of triethylaluminum (0.5 mmol/ml) and 70 mg ofthe above-mentioned solid catalyst. Polymerization was carried out fortwo hours with adjusting the molar ratio of 1-butene/ethylene in the gasphase to 0.08, hydrogen concentration to 600 ppm and total pressure to0.9 MPa by feeding the respective gases.

The polymerization activity was 350 g PE/(g catalyst-MPa-h). Theobtained ethylene copolymer had the properties of 0.23 g/10 minutes inMI, 0.9160 g/cm³ in density, 140,000 in Mw, 3.4 in Mw/Mn and 0.38 g/cm³on bulk density.

EXAMPLE 15

By using a compound of (BenzInd)₃ZrH obtained in Example 9, thepolymerization was carried out as follows.

A 100 ml flask was fed with 0.2 mmol of (BenzInd)₃ZrH obtained inExample 9, under nitrogen atmosphere, and 15 ml of toluene was added toform a toluene suspension. Subsequently, 40 mmol of methylaluminoxanesolution of a concentration of 2.9 mmol/ml (moles of Al atom) was addedand the mixture was stirred at room temperature for 10 minutes.

A 300 ml flask was fed with 10 g of SiO₂ that was sintered at 650° C.for 5 hours. The whole amount of the above-mentioned solution. wasadded. Subsequently, after the solvent was removed by nitrogen gasblowing and by reduced pressure, a fluidizable solid of catalystcomponent was obtained.

A 2.7 lit. stainless steel autoclave equipped with a stirrer wasreplaced with nitrogen gas and was maintained at 75° C. It was fed with0.3 ml of a hexane solution of triethylaluminum (0.5 mmol/ml) and 90 mgof the above-mentioned solid catalyst. Polymerization was carried outfor two hours with adjusting the molar ratio of 1-butene/ethylene in thegas phase to 0.08, hydrogen concentration to 700 ppm and total pressureto 0.9 MPa by feeding the respective gases.

The polymerization activity was 200 g PE/(g catalyst-MPa-h). Theobtained ethylene copolymer had properties of 0.52 g/10 minutes in MI,0.9200 g/cm³ in density, 100,000 in Mw, 3.2 in Mw/Mn and 0.39 g/cm³ inbulk density.

EXAMPLE 16

By using a compound of Ind₃ZrH obtained in Example 1, the polymerizationwas carried out as follows.

To a 50 ml flask were added, under nitrogen atmosphere, 0.2 mmol ofInd₃ZrH obtained in Example 1 and 10 ml of toluene to form a toluenesuspension. Subsequently, 8.7 mmol of triisobutylaluminum solution (Al:10 mmol) of a concentration of 1.15 mmol/ml (moles of Al atom) was addedand the mixture was stirred at room temperature for 10 minutes.

A 300 ml flask was fed with 10 g of layered silicate and, after dryingin vacuum at 180° C., the whole amount of the above-mentioned solutionwas added. Subsequently, after the solvent was removed by nitrogen gasblowing and by reduced pressure, fluidizable solid of catalyst componentwas obtained.

A 2.7 lit. stainless steel autoclave was equipped with a stirrer wasreplaced with nitrogen gas and maintained at 75° C. It was fed with 900ml of hexane, 1.0 ml of hexane solution of triisobutylaluminum (0.1mmol/ml), 15 ml of 1-hexene and 130 mg of the above-mentioned solidcatalyst and polymerization was carried out for two hours with adjustingthe total pressure to 0.9 MPa with feeding ethylene.

The polymerization activity was 1730 g/(g catalyst-MPa-h). The obtainedethylene copolymer had properties of 0.9 g/10 minutes in MI, 0.9269g/cm³ in density, 132,600 in Mw, 2.2 on Mw/Mn and 0.42 g/cm³ in bulkdensity.

COMPARATIVE EXAMPLE 1

The polymerization was carried out by using Ind₂ZrCl₂ as a catalystcomponent.

Into a 20 ml Schlenk tube purged by nitrogen gas, 5 ml of toluene, 5.0μmol of Ind₂ZrCl₂ and 5.0 mmol of toluene solution containing MAO(2.6mmol/ml) were added at room temperature, and the mixture was stirred for30 minutes.

A 200 ml stainless steel autoclave that was equipped with a stirrer andreplaced with nitrogen gas, was fed with 100 ml of toluene and 1.4 ml ofthe above-mentioned catalyst solution. The mixture was heated to 80° C.with stirring. Polymerization was carried out for 5 minutes withadjusting the pressure to 0.6 MPa by feeding ethylene. Thepolymerization was stopped by feeding ethanol.

Polyethylene was obtained by the polymerization, in which thepolymerization activity was 43 kg PE/(mmol Zr-MPa-h).

COMPARATIVE EXAMPLE 2

The polymerization was carried out by using Ind₂ZrCl₂.

A 100 ml flask under nitrogen atmosphere, 0.4 mmol of Ind2ZrCl₂ and 15ml of toluene was added to form a toluene suspension. Subsequently, 40mmol of methylaluminoxane solution of concentration of 2.6 mmol/ml(moles of Al atom) was added and the mixture was stirred at roomtemperature for 10 minutes.

A 300 ml flask was fed with 10 g of SiO₂ that was sintered at 400° C.for 5 hours and the whole amount of the above-mentioned solution.

Subsequently, after the solvent was removed by nitrogen gas blowing andby reduced pressure, fluidizable solid catalyst component was obtained.

A 2.7 lit. stainless steel autoclave equipped with a stirrer wasmaintained at 75° C. and was replaced with nitrogen gas. It was fed with0.25 ml of hexane solution of triethylaluminum (0.5 mmol/ml) and 130 mgof the above-mentioned solid catalyst. Polymerization was carried outfor two hours with adjusting the molar ratio of 1-butene/ethylene in thegas phase to 0.12 and the total pressure to 0.9 MPa by feeding therespective gases.

The polymerization activity was 750 g/(g catalyst-MPa-h). The obtainedethylene copolymer had properties of 0.4 g/10 minutes in MI, 0.9148g/cm³ in density, 0.38 g/cm³ in bulk density and 114.7° C. in meltingpoint.

INDUSTRIAL APPLICABILITY

The present invention provides a novel transition metal compound, whichhas not hitherto been known. The novel transition metal compound can beused as the component of catalyst for olefin polymerization havingexcellent activity. Furthermore, the transition metal compound does notcontain any halogen element, so that the olefin polymer obtained byusing the catalyst does not contain halogen element, as a result, theamount of additives such as a stabilizer can be reduced.

1. A transition metal compound represented by the following generalformula (2):(C₅R¹⁶R¹⁷R¹⁸R¹⁹R²⁰)(C₅R²¹R²²R²³R²⁴R²⁵)(C₅H₂R²⁶R²⁷R²⁸)M²H  Formula (2),wherein C₅R¹⁶R¹⁷R¹⁸R¹⁹R²⁰, C₅R²¹R²²R²³R²⁴R²⁵ and CH₅H₂R²⁶R²⁷R²⁸ denotecyclopentadienyl groups or substituted cyclopentadienyl groups,respectively; R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷and R²⁸ are any of hydrogen, a hydrocarbon group having a substituent ofa hydrocarbon having 1 to 30 carbon atoms, which are the same ordifferent; among them, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, or R²¹, R²², R²³, R²⁴,R²⁵, or R²⁶, R²⁷, R²⁸ can be bonded to one another forming a cyclichydrocarbon group, including a polycyclic structure; provided that atleast one of R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹,R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,and R²⁸ is a substituent other than hydrogen; and M² denotes atransition metal of group 4 of the periodic table.
 2. The transitionmetal compound as claimed in claim 1, wherein R²⁶, R²⁷ and R²⁸ arebonded to adjacent carbons at the 1-position, 2-position and 3-position.3. The transition metal compound represented by the following generalformula (3) as claimed in claim 1;(C₅H₂R²⁹R³⁰R³¹)(C₅H₂R³²R³³R³⁴)(C₅H₂R³⁵R³⁶R³⁷)M³H  Formula (3), wherein(C₅H₂R²⁹R³⁰R³¹), (C₅H₂R³²R³³R³⁴) and (C₅H₂R³⁵R³⁶R³⁷) denotecyclopentadienyl groups or substituted cyclopentadienyl groups,respectively; R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷are any oneof hydrogen, a hydrocarbon group having 1 to 30 carbon atoms or anorganosilicon group having a substituent of a hydrocarbon having 1 to 30carbon atoms, which are the same or different, among them, R²⁹, R³⁰,R³¹, or R³², R³³, R³⁴, or R³⁵, R³⁶, R³⁷ , can be bonded to one anotherforming a cyclic hydrocarbon group, including a polycyclic structure;provided that at least one of R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ andR³⁷ is a substituent other than hydrogen; and M³ denotes a transitionmetal of group 4 of the periodic table.
 4. The transition metal compoundas claimed in claim 3, wherein R²⁹, R³⁰, R³¹, or R³², R³³, R³⁴, or R³⁵,R³⁶, R³⁷ are bonded to adjacent carbon atoms at the 1-position,2-position and 3-position of the respective cyclopentadienyl group. 5.The transition metal compound as claimed in claim 4, wherein the threesubstituted cyclopentadienyl groups of (C₅H₂R²⁹R³⁰R³¹), (C₅H₂R³²R³³R³⁴)and (C₅H₂R³⁵R³⁶R³⁷) have the same structure.
 6. The transition metalcompound represented by the following general formula (4) as claimed inclaim 1:(C₅H₃R³⁸R³⁹)(C₅H₃R⁴⁰R⁴¹)(C₅H₃R⁴²R⁴³)M₄H  Formula (4) wherein(C₅H₃R³⁸R³⁹), (C₅H₃R⁴⁰R⁴¹) and (C₅H₃R⁴²R⁴³) denote cyclopentadienylgroups or substituted cyclopentadienyl groups, respectively: R³⁸, R³⁹,R⁴⁰, R⁴¹, R⁴² and R⁴³ are any one of hydrogen, a hydrocarbon grouphaving 1 to 30 carbon atoms or organosilicon group having a substituentof a hydrocarbon having 1 to 30 atoms, which are the same or different;among them, R³⁸, R³⁹, or R⁴⁰, R⁴¹, or R⁴², R⁴³ can be bonded to oneanother forming a cyclic hydrocarbon group, including a polycyclicstructure; provided that at least one of R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴² and R⁴³is a substituent other than hydrogen; and M4 denotes a transition metalof group 4 of the periodic table.
 7. The transition metal compound asclaimed in claim 6, wherein the three substituted cyclepentadienylgroups of (C₅H₃R³⁸R³⁹), (C₅H₃R⁴⁰R⁴¹) and (C₅H₃R⁴²R⁴³) have the samestructure.
 8. The transition metal compound represented by the followinggeneral formula (5) as claimed in claim 1;(C₉R⁴⁴R⁴⁵R⁴⁶R⁴⁷ R⁴⁸R⁴⁹R⁵⁰)(C₉R⁵¹R⁵²R⁵³R⁵⁴R⁵⁵R⁵⁶R⁵⁷)(C₉R⁵⁸R⁵⁹R⁶⁰R⁶¹R⁶²R⁶³R⁶⁴)M⁵H  Formula (5), wherein(C₉R⁴⁴R⁴⁵R⁴⁶R⁴⁷R⁴⁸R⁴⁹R⁵⁰), (C₉R⁵¹R⁵²R⁵³R⁵⁴R⁵⁵R⁵⁶R⁵⁷) and(C₉R⁵⁸R⁵⁹R⁶⁰R⁶¹R⁶²R⁶³R⁶⁴) denote indenyl groups or substituted indenylgroups, respectively; R⁴⁴ to R⁶⁴ are any one of hydrogen, a hydrocarbongroup having 1 to 30 carbon atoms or organosilicon group having asubstituent of a hydrocarbon having 1 to 30 carbon atoms, which are thesame or different, among them R⁴⁴ to R⁵⁰ or R⁵¹ to R⁵⁷ or R⁵⁸ to R⁶⁴ canbe bonded to one another forming a cyclic hydrocarbon group, including apolycyclic structure; provided that at least one of R³⁸, R³⁹, R⁴⁰, R⁴¹,R⁴² and R⁴³ is a substituent other than hydrogen; and M⁵ denotes atransition metal of group 4 of the period table.
 9. The transition metalcompound represented by the following general formula (6) as claimed inclaim 1:(C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸)(C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²)(C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶)M⁶H  Formula (6 ),wherein (C₉H₃R⁶⁵R⁶⁷R⁶⁸), (C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²) and (C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶)denote indenyl groups or substituted indenyl groups, respectively; R⁶⁵to R⁷⁶ are any one of hydrogen, a hydrocarbon group having 1 to 30carbon atoms or organosilicon group having a substituent of ahydrocarbon having 1 to 30 carbon atoms, which are the same ordifferent; among them, R⁶⁵ to R⁶⁸, R⁶⁹ to R⁷² and R⁷³ to R⁷⁶ are bebonded to carbon atoms at the 4-position, 5-position, 6-position and7-position, respectively, of the indenyl groups and they can be bondedto one another forming cyclic hydrocarbon groups, including a polycyclicstructure; and M⁶ denotes a transition metal of group 4 of the periodictable.
 10. The transition metal compound as claimed in claim 9, whereinthe three substituted indenyl groups of (C₉H₃R⁶⁵R⁶⁶R⁶⁷R⁶⁸)(C₉H₃R⁶⁹R⁷⁰R⁷¹R⁷²) and (C₉H₃R⁷³R⁷⁴R⁷⁵R⁷⁶) have the same structure. 11.The transition metal compound as claimed in claim 1, wherein thetransition metal of group 4 of the period table is Zr.
 12. A catalystfor olefin polymerization, which comprises the transition metal compoundas claimed in claim 1, an organoaluminum oxy compound and/or a compoundthat forms ion pairs with the transition metal compound.
 13. Thecatalyst for olefin polymerization as claimed in claim 12, wherein theorganoaluminum oxy compound is methyl aluminoxane.
 14. A solid catalystfor olefin polymerization, wherein the catalyst as claimed in claim 12is supported on a carrier.
 15. A solid catalyst for olefinpolymerization, wherein the transition metal compound as claimed inclaim 1 is supported on a layered silicate.
 16. A method for producing apolyolefin, wherein an olefin is polymerized in the presence of thecatalyst as claimed in claim
 12. 17. The method for producing apolyolefin as claimed in claim 16, wherein the olefin polymerization ishomopolymerization of ethylene or copolymerization of ethylene and anα-olefin.